Structure of Amorphous Materials
Solids can be crystalline or amorphous. The crystalline solid has periodic arrangement of
atoms. Crystalline solids have long range order and the character of that order is translational
periodicity. Amorphous phase or amorphous structures lack any such long range translational
order.
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Structure of Amorphous Materials 2
Structure of Amorphous Materials 3
Fig: long range order (a) and short range order (A) and (B)
But we saw that a crystal with perfect translational periodicity is an idealization. Real crystals
will have various kinds of defects. The long-range periodicity is actually broken by defects.
Similarly, a perfect disorder is also an idealization. Disordered arrangement of atoms is not
perfect and in fact, amorphous phase have what is called short range order.
The process of a liquid becoming a solid is called solidification. In solidification, the
movement of atoms slows down and they start to form an organized arrangement, or lattice
structure. The formation of the lattice structure is driven by the decrease in thermal energy,
which leads to the reduction in random motion of the atoms. In the case of crystalline solids,
the atoms arrange in a repeating pattern to form a crystal lattice. In non-crystalline solids, the
atoms do not form a repeating pattern and instead form a random arrangement
Three factors contributing to crystal formation are:
1. Mobility of atoms/compounds in the liquid phase (High mobility leads to crystal
formation)
2. Complexity of the solid crystal structure (Simple structure results in crystal formation)
Structure of Amorphous Materials 4
3. Cooling rate (Slow cooling results in crystal formation).
Solids can be classified as either crystalline or amorphous. Crystalline solids have a periodic
arrangement of atoms and have long-range order, while amorphous solids have no such
pattern and are considered disordered. However, it is important to note that real crystals have
defects that disrupt their long-range periodicity. Similarly, true disorder is an idealization as
amorphous solids still have some short-range order.
"Silica (SiO2) is one of the most abundant minerals in the Earth's crust and can exist in either
crystalline or amorphous form. When silica is crystalline, it can exist in various phases, such
as quartz. Conversely, if the silica unit are disordered and not arranged in an orderly fashion,
the result is amorphous silica, commonly known as glass.”
The basic building block of both crystalline and amorphous silica is known as the silicate
tetrahedron. The tetrahedron consists of a silicon atom, that is bonded to four oxygen atoms
located at the corners of a tetrahedron.
While the composition of silica is SiO2, the composition of the silicate tetrahedron is Sio4,
which includes more oxygen than silica. Additionally, the electrical charges of the silicon
atom and oxygen atoms in the tetrahedron are imbalanced, with the silicon atom having a
positive charge of 4 and each oxygen atom having a negative charge of 2. This results in a net
negative charge of 4, which is why the silicate tetrahedron is known as having a charge of 4
minus.
Fig: Silica Tetrahedra
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The silica tetrahedra forms a corner-sharing network. This refers to the sharing of corner
oxygen atoms between adjacent tetrahedra, effectively dividing the oxygen contribution from
each corner between two tetrahedra. Each tetrahedron in this network will receive half of the
oxygen from each of its four corners.
This corner sharing results in a balanced composition, with each tetrahedron consisting of
two oxygen atoms and one silicon atom. Additionally, the shared oxygen atoms in the
network provide only half of their charge to each tetrahedron, which results in a neutral
charge balance of -4 from oxygen and +4 from silicon.
Fig: Corner shared silica tetrahedra
Silica tetrahedra form a corner sharing network, which can either be periodic or random. A
periodic network results in crystalline silica, such as quartz, while a random network results
in amorphous silica, also known as glass. Pure silica glass without any additives is referred to
as fused silica glass.
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Fig: Glass
Fig: Quartz
The schematic representation shown is of a random network of silicate tetrahedra in the fused
silica glass. In this representation, each triangle with border lines represents a tetrahedron and
the corners (location of oxygen atoms) are shared between two tetrahedra. The bonds in the
network are a mixture of covalent and ionic bonds and are strong, leading to a stiff glass with
a high melting point. The high cost of processing fused silica glass results in its limited use,
mainly for high temperature applications like furnace windows. To reduce cost and melting
point, additives are added to produce soda lime glass which is more commonly used for
ordinary windows.
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Soda lime glass is a type of glass that contains sodium oxide (Na2O) as an additive. This
additive helps modify the network of silicate tetrahedra, which are the building blocks of the
glass. Na2O provides an extra oxygen that breaks the corner bond between two tetrahedra,
allowing them to separate. The extra oxygen from Na2O helps balance the valencies of the
oxygen and silicon atoms. However, this results in weak secondary bonds (van der Waals
bonds) between the tetrahedra instead of strong primary bonds. This leads to a lower melting
point, making the processing of soda lime glass cheaper than fused silica glass. Therefore,
soda lime glass is commonly used for windows because of its lower cost and processing
temperature.
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