Chemistry for Everyone
Glass Doesn’t Flow and Doesn’t Crystallize
and It Isn’t a Liquid
Stephen J. Hawkes
Department of Chemistry, Oregon State University, Corvallis, OR 97331-4003; stephen.hawkes@orst.edu
Glass is widely believed to flow in historic time, and there
are science teachers who believe it. As a beginning teacher I
taught it myself. Mea culpa. It has been asserted in the popular
press (1, 2) and even in scientific literature and introductory
texts (3–5). This paper reviews the evidence and reaches the
conclusions in the title.
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Historic Glass
One approach to this enquiry is to ask conservators who
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routinely work with antique glass whether they have observed
it overlapping the fixtures at the bottom of the glass, or
whether the glass is thinner at the center of glass windows
where the flow would be greatest than at the edges where it
would be slowest, and whether there is thicker glass at the
bottom. They have denied repeatedly and consistently that they
have observed such phenomena (6–8; personal communication
with Moore, D., Colonial Williamsburg Foundation). Gibson
states that in a lifetime of dismantling medieval glass he has seen
hundreds of pieces that were thicker at the top (7). So it is
unnecessary to invoke the “explanation” that artists setting
the glass pieces would be likely to set the thicker part lower.
No statistical study of thickness of old window glass has
ever been found. In the light of their experience, glass scientists
are unlikely to undertake such research. A report on colonial
glass at Williamsburg describes how the method of manu-
facture necessarily produced uneven glass, which would be
thicker in some places than in others (9).
Flow in Prolonged Time
If glass showed perceptible flow in a few centuries, then
some volcanic glasses would show substantial flow in geo-
logic time. It would penetrate crevices in other rocks and form
blobs of flattened glass. The discovery of such formations
would be clear evidence of flow (albeit very slow flow) but such
phenomena have not been reported.1 Similarly, astronomical
mirrors show no deformity after standing for more than a
century, although it is asserted that expected deformation
from the alleged flow would be observable and ruinous (4 ).
Flow under High Pressure?
Bridgman provided evidence on this question by his
experiments on glass under extreme pressure (10, 11). He
found that there was a short period of flow as the glass was
compressed but then no further flow. When flow was pre-
vented, the glass could not be compressed. So there is no
flow in the normal sense of the word but the phenomenon is
better interpreted as a molecular rearrangement.
846 Journal of Chemical Education • Vol. 77 No. 7 July 2000 • JChemEd.chem.wisc.edu
Surface Flow
A curious type of flow has been reported in the surface
layer of glass that has been rapidly cooled. When glass is
scratched with a fine diamond point, several surface effects
have been observed, one of which—on glass that has cooled
quickly—is a form of surface flow. Peychès explains that
“There exists a surface skin of more or less appreciable
thickness in which the molecules are less strongly bonded
than in the rest of the mass of the glass, which has been chilled
less rapidly. In these surface layers viscous flow takes place
when the glass is subject to stress at low temperature. Only
fine annealing can cause such mobility to disappear” (12). If
this really is regular viscous flow, it follows that there is a
form of glass which, if it could be created in bulk, would
flow under pressure. However, it could not apply to ancient
window glass or any other glass that presently exists.
Glass workers know that in order to cut glass it is necessary
to break it at a scratch that has been made no more than two
minutes earlier. Otherwise it will heal, appearing the same
but losing its ability to guide the crack (13). It has been
suggested that this is the result of glass flow in the freshly
made groove, but it seems more likely that it is related to the
formation of the hydrated layer, which is known to occur
within five minutes (14).
Measurement of Viscosity of Cold Glass
There is a rumor that the viscosity of cold glass has
actually been measured. I have been unable to find any
literature reference to such measurement and none of the
people who suggested it to me has been able to supply a clue
that leads me to one. Literature values that I have found have
in every case been the result of extrapolation from high
temperatures. If any reader provides a clue that leads me to a
viscosity measurement on cold glass, I will offer the editor a
retraction.
Such a measurement would have to measure actual flow
against a much greater background of anelastic deformation
and would also have to allow for changes in the
microstructure of the glass during the experiment. I believe
this is not possible with present technology. A review of
various methods of determining glass viscosity (15) shows
none that is useful above 1015 Pa s, so the much higher values
reported for cold glass must presumably be obtained by
theoretical extrapolation.
No evidence for the flow of cold glass can be found from
viscosity measurement using present technology. There is no
evidence to support a belief that viscosity could be measured
with sufficiently sensitive technology at some future time.

Supercooling
It is often asserted that glass is a supercooled liquid. When
molten glass is cooled it eventually adopts the glassy state at
the “glass transition temperature”. This temperature varies
with the rate of cooling so that the material may be a liquid
at the same temperature at which, under other circumstances,
it would be a glass. Such a liquid is said to be “supercooled”
and eventually undergoes the glass transition at a lower
temperature than if it had not supercooled. The properties
of the supercooled liquid are a simple extrapolation of the
properties of the melt until it reaches the glass transition. At the
glass transition the rate of change of most physical properties
with temperature undergo a sharp transition: specifically, the
graphs of length and of heat capacity and especially of entropy
against temperature have marked changes in slope (16 ). Cool
glass is substantially different from the supercooled liquid
(even at the same temperatures) in these and other measurable
properties, as well as in the obvious properties that are known
to artisan glass workers.
Deformation
When glass is stressed it undergoes an immediate elastic
deformation, which is followed by a slow inelastic deformation.
When the stress is removed, the glass reverts to its original state.
Since the inelastic reversion is slow, this has sometimes been
mistaken for a permanent deformation and used as evidence
for flow or that glass is a liquid. Spencer’s classic experiment
shows that this claim is a misinterpretation (17, 18).
The earliest reference to this kind of phenomenon that
has come to light was the statement by Ostwald in an 1893
text that glass tubing “must be kept lying flat, otherwise it
becomes permanently curved” (19). The later work of Rayleigh
and others shows that this is untrue (20).
Crystallization (Devitrification)
It is also widely believed that glass crystallizes spontane-
ously in historic time. One recent introductory science text (now
replaced by a later edition) had a picture of an Egyptian glass
bowl with some white patches, which were said to be incipient
crystallization. However, deterioration of glass is the result
of attack by water or water vapor (14 ). This causes a crust of
hydrated silica, which appears as a white surface on the glass.
This may be followed by further chemical action such as
leaching of the metal ions or attack by carbon dioxide, causing
further deterioration, which appears as further encrustation
or pits. Glass displayed in museums has been known to dete-
riorate visibly in as little as a few months when the humidity
is not carefully controlled (21). In geologic time this process
converts volcanic glass to perlite, an opalescent hydrate of
the original glass (22).
A better test of crystallization over geologic time would
be to examine glass from extraterrestrial bodies that have no
atmosphere to corrode it. Particles of moon glass have micro-
scopic pits and grooves that appear to be the result of micro-
meteorites striking the glass surfaces (23), but no example
has been reported of moon glass that has visibly crystallized
after it has cooled. Future crystallographic examination
JChemEd.chem.wisc.edu • Vol. 77 No. 7 July 2000 • Journal of Chemical Education
Chemistry for Everyone
may show microcrystallites, and this would be evidence of
geologically slow crystallization.
Such a possibility is addressed theoretically by Kny and
Nauer (24 ). They calculated that crystallization could not
reach a volume fraction of 10᎑6 in less than 1000 years under
the most favorable conditions, and 106 to 1017 years under
realistic conditions. Newton quotes them as believing that
they have found microcrystallites about 20 nm in size in early
medieval glass, but comments “However, if so, it is so rare as
to be negligible” (25). There has been no subsequent report
of such microcrystallites in antique glass. Kny and Nauer also
quote Besborodov (26 ) as saying that obsidian has many
crystalline inclusions, whereas tektite samples do not. They
account for this by the larger concentration of OH groups
in the obsidian, which has 100 times more water than the
tektites. If crystallization depends on the presence of water,
the crystals may be perlite rather than crystallized glass. Such
microcrystallites would be significant in glass science, but would
not be relevant to the visible deterioration of antique glass.
Students should not be taught that crystallization can
occur in historic time. Deterioration in ancient glass is explained,
by those best qualified to discuss the matter, as the result of
chemical attack, a phenomenon that has been the subject of
much research (14 ).
Structure of Glass
The belief that glass is a liquid is often supported by the
assertion that its molecular structure is random like a liquid’s.
Glass actually has a number of states with entropy minima,
which are therefore nonrandom (27). They can be interconverted
by heat, pressure or strain. A well-known example of such
interconversion is “annealing”. If liquid glass is cooled quickly
it solidifies in a molecular arrangement that is unstable and
may shatter spontaneously. Glassblowers routinely transform
this into a more stable state by annealing it at a temperature
below the melting point.
Angell gives the following theoretical denial in an authori-
tative paper on the physics of glass (16 ):
The fact that glasses are brittle solids at temperatures
below their glass transition temperatures implies that the
arrangement of particles taken up as a liquid cools below
Tg can be described by a point in configuration space
near the bottom of a potential energy minimum in this
space. If this were not so, the system would move in the
direction dictated by the collective unbalanced force
acting on it, and some sort of flow would occur. Not-
withstanding the legend about medieval cathedral windows,
this does not occur in glassy systems held at temperatures
less than half their glass transition temperatures, even on
geological time scales.
Rather than having an amorphous arrangement, glasses
form as a weak reflection of a three-dimensional crystal
structure, which is so energetically incompetent that it can
barely compete with the disordered form (16 ). Texts routinely
show diagrams contrasting the regular hexagonal arrangement
of crystalline silica with a less ordered arrangement of contigu-
ous polygons of varying size in glass. Such an arrangement is as
rigid as the silica, but perhaps less stable thermodynamically.
847
 Chemistry for Everyone
So?
Whether glass is a liquid must depend on its ability to
flow, or to spontaneously adopt a new conformation of equal
energy. This has not been demonstrated either theoretically
or experimentally, so an assertion that cold glass is a liquid
must be regarded as incorrect.
Students should not be taught that glass is a liquid because
such teaching creates a mental concept that is divorced from
reality. It leads inevitably to the fallacies that glass flows or
crystallizes after a long enough time. Even if a sensible argu-
ment could be discovered that glass is a liquid in some esoteric
sense, it would create more confusion than enlightenment.
Glass is a rigid solid with a lower degree of molecular
order (higher entropy) than a crystal but with greater molecular
order (lower entropy) than a liquid.
Note
1. It has been argued that volcanic glass has a higher silica con-
tent than historic window glass and would therefore have greater
viscosity, flow more slowly, and perhaps not be deformed even in
geologic time. Actual data do not support this. Tables of composi-
tion of geological glasses give silica content varying from 35 to 76%,
whereas the SiO2 content of antique glass varies from 50 to 75%.
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