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Is glass liquid or solid?

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 Is glass liquid or solid?
By Philip Gibbs
Abstract: It is sometimes said that glass in very old churches is thicker at the
bottom than at the top because glass is a liquid, and so over several centuries it
has flowed towards the bottom. This is not true. In Mediaeval times panes of
glass were often made by the Crown glass process. A lump of molten glass
was rolled, blown, expanded, flattened and finally spun into a disc before
being cut into panes. The sheets were thicker towards the edge of the disc and
were usually installed with the heavier side at the bottom. Other techniques of
forming glass panes have been used but it is only the relatively recent float
glass processes which have produced good quality flat sheets of glass.
Nevertheless, the frequently asked question “Is glass liquid or solid?” is not so
straightforward to answer. To do so we have to understand its thermodynamic
and material properties.

Thermodynamics of glass

There is still much about the molecular physics and thermodynamics of glass that
is not well understood, but we can give a general account of what is thought to be
the case.

Many solids have a crystalline structure on microscopic scales. The molecules are
arranged in a regular lattice. As the solid is heated the molecules vibrate about
their position in the lattice until, at the melting point, the crystal breaks down and
the molecules start to flow. There is a sharp distinction between the solid and the
liquid state, that is separated by a first order phase transition, i.e. a discontinuous
change in the properties of the material such as density. Freezing is marked by a
release of heat known as the heat of fusion.
 molecular arrangement in a crystal

A liquid has viscosity, a measure of its resistance to flow. The viscosity of water at
room temperature is about 0.01 poises. A thick oil might have a viscosity of about
1.0 poise. As a liquid is cooled its viscosity normally increases, but viscosity also
has a tendency to prevent crystallisation. Usually when a liquid is cooled to below
its melting point, crystals form and it solidifies; but sometimes it can
become supercooled and remain liquid below its melting point because there are
no nucleation sites to initiate the crystallisation. If the viscosity rises enough as it
is cooled further, it may never crystallise. The viscosity rises rapidly and
continuously, forming a thick syrup and eventually an amorphous solid. The
molecules then have a disordered arrangement, but sufficient cohesion to maintain
some rigidity. In this state it is often called an amorphous solid or glass.

molecular arrangement in a glass

Some people claim that glass is actually a supercooled liquid because there is no
first order phase transition as it cools. In fact, there is a second order
transition between the supercooled liquid state and the glass state, so a distinction
can still be drawn. The transition is not as dramatic as the phase change that takes
you from liquid to crystalline solids. There is no discontinuous change of density
and no latent heat of fusion. The transition can be detected as a marked change in
the thermal expansivity and heat capacity of the material.

The temperature at which the glass transition takes place can vary according to
how slowly the material cools. If it cools slowly it has longer to relax, the
transition occurs at a lower temperature and the glass formed is more dense. If it
cools very slowly it will crystallise, so there is a minimum limit to the glass
transition temperature.

Density as a function of temperature

in the phases of glassy materials

A liquid to crystal transition is a thermodynamic one; i.e. the crystal is

energetically more favourable than the liquid when below the melting point. The
glass transition is purely kinetic: i.e. the disordered glassy state does not have
enough kinetic energy to overcome the potential energy barriers required for
movement of the molecules past one another. The molecules of the glass take on a
fixed but disordered arrangement. Glasses and supercooled liquids are both
metastable phases rather than true thermodynamic phases like crystalline solids. In
principle, a glass could undergo a spontaneous transition to a crystalline solid at
any time. Sometimes old glass devitrifies in this way if it has impurities.
The situation at the level of molecular physics can be summarised by saying that
there are three main types of molecular arrangement:

crystalline solids: molecules are ordered in a regular lattice

fluids: molecules are disordered and are not rigidly bound.
glasses: molecules are disordered but are rigidly bound.

[Just to illustrate that no such classification could ever be complete, recently

scientists have succeeded in making quasi-crystals that are quasi-periodic. They
do not fit into the above scheme and are sometimes described as being halfway
between crystals and glass.]

It would be convenient if we could conclude that glassy materials changed from

being a supercooled liquid to an amorphous solid at the glass transition, but this is
very difficult to justify. Polymerised materials such as rubber show a clear glass
transition at low temperatures but are normally considered to be solid in both the
glass and rubber conditions.

It is sometimes said that glass is therefore neither a liquid nor a solid. It has a
distinctly different structure with properties of both liquids and solids. Not
everyone agrees with this terminology.

Material properties of glasses

Usually when people talk about solids and liquids, they are referring to
macroscopic material properties rather than the arrangement of molecules. After
all, glass as a material was known about long before its molecular physics was
understood. Macroscopically, materials exhibit a very wide range of
behaviours. Solids, liquids and gases are ideal behaviours characterised by
properties such as compressibility, viscosity, elasticity, strength and hardness. But
materials don't always behave according to such ideals. For example, it's possible
to take water from being a liquid to a gas at high pressure without its passing
through a phase transition; so at some stage it must be between an ideal liquid and
an ideal gas.

For crystalline substances the distinction between the solid and liquid states is very
clear, but what about glasses? Indeed, where do polymers, gels, foams, liquid
crystals, powders and colloids fit into this picture? Some people say that there is
no clear distinction between a solid and a liquid in general. A solid, they claim,
should just be defined as a liquid with a very high viscosity. They set an arbitrary
limit of 1013 poises above which they say it's a solid and below which it's a liquid.
According to another point of view, this ignores a distinction between viscosity of
liquids and plasticity of solids. An ideal Newtonian liquid deforms at a rate which
is proportional to stresses applied and its viscosity. For arbitrarily small stresses a
viscous liquid will flow. Molasses, pine pitch and Silly Putty are examples of
liquids with very high viscosity that flow very slowly under only the force of their
own weight. On the other hand, plastics can be very soft but are still considered
solid because they have rigidity and do not flow.

Solids are elastic when small stresses are applied. They deform but return to their
original shape when the stress is removed. When higher stresses are applied some
solids break while others exhibit plasticity. Plasticity means that they deform and
don't return to their original shape when the stress is removed. Many substances
including metals such as copper have plasticity. The resistance to flow under
plastic deformation is called its viscoplasticity. This is like viscosity, except that
there's a minimum stress known as the elastic limit below which there is no
plasticity. Materials with plasticity do not flow, but they may creep, meaning they
deform slowly but only when held under constant stress.

So an arbitrary measure of viscosity or viscoplasticity is not a good way to

distinguish solids from liquids. Another way to define the distinction between
solid and liquid is to say that, if there is a minimum shear stress required to
produce a permanent deformation then it is a solid. This is just a precise way of
saying it has some rigidity. A liquid can then be defined as a material that will
flow. If it is placed in a container it will eventually flow to fill the lower reaches
until its own surface is flat. The difficulty is that these two definitions do not cover
all cases. There are materials that have some limited flow known as
viscoelasticity. The material will deform elastically under stress. If the stress is
held for a long time, the deformation becomes permanent even if the stress was
small. Materials with viscoelasticity may seem to flow slowly for a while but then
stop. It is futile to try to make a clear cut distinction between liquids and solids in
cases of such behaviour.

Types of Glass

To be sure that glass in old windows has not flowed, we need to recognise the
different properties of different glasses. Glass can be made from pure silica, but
fused silica has a high glass transition point at around 1200° C which makes it
difficult to mould into panes or bottles. At least 2000 years ago it was learned how
to lower the softening temperature by adding lime and soda before heating, which
resulted in a glass containing sodium and calcium oxides. Soda-lime glass used for
windows and bottles today contains other oxides as well. Measuring the glass
transition temperature for different glasses is not easy because it changes according
to how slowly the glass is cooled. In the case of modern soda-lime glass, a quick
cooling will produce a glass transition at about 550° C. There is thought to be a
minimum glass transition temperature at about 270° C, and if it is cooled very
slowly it can still be a supercooled liquid down to just above that
temperature. Glass such as Pyrex (used for test-tubes and ovenware) is usually
based on boro-silicates or alumino-silicates, which withstand heating better and
typically have a higher glass transition temperature. Some glasses, such as the
leaded variety, have lower transition temperatures.

Sometimes people say that good evidence that glass does not flow is provided by
telescope lenses which after 150 years still maintain excellent optical
qualities. They would be spoiled by the slightest deformation. In fact, optical
glass is usually not the same as the glass used in windows and bottles. It may be
based on boro-silicate or soda-lime glass with other metallic oxides added to
improve its thermal and optical properties. So old telescope lenses and mirrors
provide good evidence that some glasses do not flow, but little evidence to support
the claim that glass in old windows has not flowed. Another example is Stone Age
arrow heads made of obsidian, a natural glass. These are found to be still razor
sharp after tens of thousands of years, but again, this glass is mainly silica and
alumino-silicates and is much tougher than window glass.

For definitive evidence that glass has not flowed in old windows we must examine
the oldest examples. Early glass used to make bottles and windows was usually
formed by adding soda and lime to silicates. Sometimes potash was added
instead. Usually there were other impurities that made it softer than modern soda-
lime glass. Other compounds were often added to give colour or to improve its
properties. The Romans were making glass objects of this sort in the 1st century
AD, and despite being very delicate, some examples remain—such as the
elaborately decorated Portland Vase kept at the British Museum. Roman
glassware provides some of the best available evidence that types of soda-lime
glass are not fluid, even after nearly 2000 years. The oldest remaining examples of
stained glass windows that remain in place have lasted since the 12th century. The
oldest of all are the five figures in the clerestory of Augsburg Cathedral in
Germany, which are dated to between 1050 to 1150. Many other early examples
are found in France and England including the magnificent North Rose window of
Notre Dame, Paris dating from 1250.

There have been many claims (especially by tour guides) that such glass is
deformed because the glass has flowed slowly over the centuries. This has become
a persistent myth, but close inspection shows that characteristic signs of flow, such
as flowing around, and out of the frame, are not present. The deformations are
more consistent with imperfections of the methods used to make panes of glass at
the time. In some cases gaps appear between glass panes and their frames, but this
is due to deformations in the lead framework rather than the glass. Other examples
of rippling in windows of old homes can be accounted for because the glass was
imperfectly flattened by rolling before the float glass process came into use.

It is difficult to verify with absolute certainty that no examples of glass flow exist,
because there are almost always no records of the original state. In rare cases
stained glass windows are found to contain lead, which would lower the viscosity
and make them heavier. Could these examples deform under their own
weight? Only careful study and analysis can answer this question. Robert Brill of
the Corning glass museum has been studying antique glass for over 30 years. He
has examined many examples of glass from old buildings, measuring their material
properties and chemical composition. He has taken a special interest in the glass
flow myth and has always looked for evidence for and against. In his opinion, the
notion that glass in Mediaeval stained glass windows has flowed over the centuries
is untrue and, he says, examples of sagging and ripples in old windows are also
most likely physical characteristics resulting from the manufacturing
process. Other experts who have made similar studies agree. Theoretical analysis
based on measured glass viscosities shows that glass should not deform
significantly even over many centuries, and a clear link is found between types of
deformation in the glass and the way it was produced.

Conclusion
There is no clear answer to the question "Is glass solid or liquid?". In terms of
molecular dynamics and thermodynamics it is possible to justify various different
views that it is a highly viscous liquid, an amorphous solid, or simply that glass is
another state of matter that is neither liquid nor solid. The difference is
semantic. In terms of its material properties we can do little better. There is no
clear definition of the distinction between solids and highly viscous liquids. All
such phases or states of matter are idealisations of real material
properties. Nevertheless, from a more common sense point of view, glass should
be considered a solid since it is rigid according to everyday experience. The use of
the term "supercooled liquid" to describe glass still persists, but is considered by
many to be an unfortunate misnomer that should be avoided. In any case, claims
that glass panes in old windows have deformed due to glass flow have never been
substantiated. Examples of Roman glassware and calculations based on
measurements of glass visco-properties indicate that these claims cannot be
true. The observed features are more easily explained as a result of the imperfect
methods used to make glass window panes before the float glass process was
invented.
 References

"Antique windowpanes and the flow of supercooled liquids", by Robert C. Plumb,

(Worcester Polytech. Inst., Worcester, MA, 01609, USA), J. Chem. Educ. (1989),
66 (12), 994–6

Ernsberger, F. M. "In Glass: Science and Technology"; D.R. Uhlmann, N.J.

Kreidle, Eds; Acad. New York, 1980; Vol. V, Chapter 1.

"Physics of Amorphous Materials" by S.R. Elliott (London: Longman Group Ltd,

1983)

C. Austin Angell, Science, March 1995

Robert H. Brill, "A Note on the Scientist's definition of glass", Journal of Glass
Studies, vol. 4, 127–138, 1962

Florin Neumann, "Glass: Liquid or Solid — Science vs an Urban Legend"

"Do Cathedral Glasses Flow?", Am. J. Phys. v66, pp 392–396, May 1998

Edgar Zanotto, American Journal of Physics 66 p392, May 1998

Paul Steinhardt, "Crazy Crystals", New Scientist, 25 January 1997

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