Ch.

Amorphous Structures
Course KGP003

High Temperature Materials

By
Docent. N. Menad

Dept. of Chemical Engineering

and Geosciences Div. Of
process metallurgy

Lule University of Technology

( Sweden )
 Amorphous Materials

An amorphous solid is a solid in which there is no long-range order of the positions

of the atoms. (Solids in which there is long-range atomic order are called crystalline
solids.) Most classes of solid materials can be found or prepared in an amorphous
form. Ex:
common window glass is an amorphous ceramic, many polymers (such as
polystyrene) are amorphous, and even foods such as cotton candy are amorphous
solids.

Amorphous materials are often prepared by rapidly cooling molten material. The
cooling reduces the mobility of the material's molecules before they can pack into a
more thermodynamically favourable crystalline state. Amorphous materials can also
be produced by additives which interfere with the ability of the primary constituent to
crystallize. For example addition of soda to silicon dioxide results in window glass
and the addition of glycols to water results in a vitrified solid.

Some materials, such as metals, are difficult to prepare in an amorphous state. Unless
a material has a high melting temperature (as ceramics do) or a low crystallization
energy (as polymers tend to), cooling must be done extremely rapidly.
Amorphous solids can exist in two distinct states, the 'rubbery' state and the 'glassy'
state. The temperature at which the transition between the glassy and rubbery states is
called their glass transition temperature or Tg.
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Amorphous structures of inorganic glass, even called vitreous state, can be

defined as follows:
An isotropic material that does not have long range 3-dimensional atomic
periodicity (after 20 ) and has a viscosity greater than 1014 poise.

The difference between a glass and its corresponding liquid

can be demonstrated by the volume/temperature relationship
during cooling shown in the diagram to the right. During
cooling of a melt to its crystallization temperature (melting
temperature) Tm, the volume follows line a. When the
crystallization doesnt occur the volume follows line b and
a super-cooled liquid is formed. After further cooling, line
b changes to line c with an inflection point at the glass
transition temperature, Tg, resulting in the formation of a
glass. Due to the high viscosity of super-cooled melts,
cooling must occur extremely slowly if the cooling curve is to
show a distinct inflection point. Otherwise, the
volume/temperature relationship follows a curve like line d.
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When a crystalline material is heated, the melting temperature

(TM) is well defined. But on cooling, it is often possible to
undercool the liquid so that nucleation and growth do not occur.
At a temperature below TM, the material can become rigid and
act like a solid, while preserving the amorphous atom
arrangement.

This is called the glass transition temperature Tg. A plot of volume of density is often used to
illustrate this, since the expansion coefficient of the liquid, crystalline solid, and amorphous solid are
all generally different.

In real materials, Tg depends on cooling rate, and many other

secondary factors, and may not show such a sharp transition
as indicated here
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Glass can be classified as a super-cooled liquid in which

crystallization has not occurred. There are quite many similarities
between glass and liquids.

Glass structure is however much more complicated than crystal

structure. Glass has properties that are difficult or impossible to
simulate in crystalline material. These properties are also
continuously variable in a way that is impossible for a crystalline
material as well.
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A kinetic theory which describes the transition of a melt to a

glass is based on the slow nucleation of crystal grains and
subsequent polycrystalline growth. The rate of nucleation is, as
well as crystal growth rate, temperature dependent but the rate
controlling functions contain conflicting terms that lead to the
different functions having distinct rate maxima, see adjacent
diagram..

As soon as a nucleation has begun, a crystal will start to grow at

a certain rate depending on the rate of atomic diffusion to the
crystal surface. Crystal growth is therefore dependent on the
viscosity of the melt. Crystal growth rate reaches a maximum,
which for glass, often lies at a different temperature than the
maximum nucleation rate. Also noteworthy, is that the activation
energy for nucleation as well as crystal growth within glass
systems is higher than the Gibbs free activation energy for
viscous flow or self-diffusion

This phenomenon can be explained by the
fact that bonds within a molecular unit
must be broken to allow for crystallization
to occur
Tendency to glass formation increases with:
Increased cooling rate
Increased surface tension melt/crystalline phase
Increased transformation temperature
Decreased melt volume
Decreased grain density
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Metallic Glass
Some amorphous metallic alloys can be prepared under special processing conditions (such as rapid
solidification, thin-film deposition, or ion implantation), but the term "metallic glass" refers only to
rapidly solidified materials.

Even with special equipment, such rapid cooling is required that, for most metals, only a thin wire or
ribbon can be made amorphous. This is enough for many magnetic applications, but thicker sections
are required for most structural applications such as scalpel blades, golf clubs, and cases for
consumer electronics.

Recent efforts have made it possible to increase the maximum thickness of glassy castings, by
finding alloys where kinetic barriers to crystallization are greater. Such alloy systems tend to have the
following inter-related properties:

Many different solid phases are present in the equilibrium solid, so that any potential crystal will find that
most of the nearby atoms are of the wrong type to join in crystallization.
The composition is near a deep eutectic, so that low melting temperatures can be achieved without
sacrificing the slow diffusion and high liquid viscosity seen in alloys with high-melting pure
components
. Atoms with a wide variety of sizes are present, so that "wrong-sized" atoms interfere with the
crystallization process by binding to atom clusters as they form. One such alloy is the
commercial "Liquidmetal", which can be cast in amorphous sections up to an inch thick
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With the help of X-ray diffraction studies, the structure of glass
is shown to be based on SiO4 tetrahedral units that are bound to
GLASS STRUCTURE
each other in a random network with so called modified atom
species spread throughout void spaces, as seen in the adjacent
schematic. Here one notices that certain Si-O-Si bonds are
broken and replaced by free O-endings and metal cations
according to the following formula:

M+
- Si O Si- + M2O -Si-O- O- - Si-
M+

A requirement in oxide glass formation is the possibility to

form a 3-dimensional structural network with a comparable
energy to that needed for a corresponding crystalline structural
network. This requires that the primary coordinate number for
every atom in the glass should be nearly identical to those in
the crystalline material. Furthermore, the secondary coordinate
should have only a very small contribution to the total
structural energy. Consider SiO2 for example, the structural
energy difference between Cristobalite and glassy SiO2 (Quartz
glass) is only ~1%
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Structures found from the glass beads demonstration. A perfect crystal (a),
an amorphous structure (b), and a crystal with a vacancy (c) is shown
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A B C

The amorphous state The crystalline state An intermediate state

obtained by a rapid obtained after a long in the cooling process,
quench from a random slow cooling with which after reheating
start to a temperature occasional heating eventually resulted in
just above T= 0 a picture similar to B.
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To fulfill these requirements, Zachariassen has proposed the following

necessities for oxide glass formation.

1. Every oxygen atom should not be bound to more than two cations.

2. The coordinate number for oxygen ions positioned around the

central cation should be small, i.e. less that 4.

3. Oxygen polyhedra can share a corner with each other in order to

form a 3-dimensional network. However, the polyhedra can not share
common edges or surfaces.

4. At least 3 corners of every polyhedron should be shared.

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The viscosity is a crucial factor in glass

formation.

Glass formation is favorable in a material

when:

1. The viscosity is high at the melting point.

2. The viscosity below the melting point

increases with decreasing temperature.

The glass transition temperature, Tg, and the melting temperature, Tm, were
introduced and which are also present in the given diagram. Normally, the
two temperatures have the following relationship

Tg2/3*Tm
Tg 2/3*Tm
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VISCOSITY OF GLASS
The viscosity is, as mentioned, also very dependent
on composition. In silicate glass, the viscosity
decreases with increasing content of modified
cations. In many cases the change is very
pronounced. For example, for a quartz glass (pure
SiO2) at 1700C the viscosity decreases 104 poise
with an addition of as little as 2.5 mol% K2O.

This effect can be attributed to the presence of

oxygen atoms that only have one bond and cause a
weak link in the Si-O- network. In the adjacent
diagram, the effect of replacing 8% of SiO2 in a
74SiO2-10CaO-16Na2O glass with different divalent
oxides to the viscosity at 1400C is shown.

For Borsilicate glass, the change in viscosity with an addition of alkali oxides is more
complicated. At high temperatures the viscosity decreases with increased alkali addition,
whilst at lower temperatures, the viscosity increases with increased alkali addition. This
phenomenon has yet to be explained theoretic.
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Thermal Stress in Glass

It is understandable that thermal stresses occur between

materials with different thermal expansion behavior during
heating and cooling. When considering glass materials,
thermal stresses can occur when different parts of the glass,
having different specific volumes, cool at different rates.
This is the case when a glass product contains segments
with diverse cross sections. Naturally, a thick material will
cool faster than a thin material. A glass material that is
cooled rapidly at the surface will suffer thermal stress
between the surface and interior.
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When reheating the glass the volume curve will

follow the same curve as mentioned above but in
the opposite direction.
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The next diagram illustrates the behavior of 3 different
glasses; A, B and C, with different specific volumes (i.e.
different cooling rates) in terms of temperature vs.
physical expansion. Glass A is a rapidly cooled glass, B
a moderately cooled glass, C a slowly cooled glass.

The diagram demonstrates that the thermal expansion

coefficient is the same for all 3 glasses at temperatures
up to 400C, i.e. the curves are parallel. Above 400C,
glass A contracts up to roughly 560C until the glass
structure has reached equilibrium, i.e. the specific
Viscosity of glass at
volume of the slowly cooled glass. On the other hand,
different temperature
glass C follows the normal glass cooling curve from
the opposite direction which maintains that the structure
Annealing temperature
in this glass is in equilibrium during the entire course of
which is a characteristic
cooling.
property for every glass

It is through the use of thermal treatment at temperatures near the annealing temperature
that thermal stresses in glass can be eliminated. This is a standard practice in
manufacturing of glassware with varying thickness, for example; drinking glass, glass
bottles and so on.
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GLASS CHEMICAL COMPOSITIONS

Chemical composition , Wt.%

Type of Glass
SiO2 Al2O3 CaO MgO Na2O K2O PbO B2O3

Window glass 72 1.3 8 4 14 0.3

Packing glass 72 0.1 5 4 15

Borsilicate glass 80 2 4 13

Lead glass 54 1 8 37

(Crystal glass)
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TYPES OF COMMERCIAL GLASS

WINDOW GLASS
PLATE GLASS
BOTTLES AND CONTAINERS
OPTICAL GLASS
PHOTOSENSITIVE GLASS
GLASS CERAMICS
GLASS FIBERS
MISCELLANEOUS TYPES OF GLASS
RECYCLING GLASS
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RECYCLING GLASS

Scrap glass taken from the glass manufacturing process, called cullet, has been
internally recycled for years. The scrap glass is economical to use as a raw material
because it melts at lower temperatures than other raw materials, thus saving fuel and
operating costs.

Glass that is to be recycled must be relatively free from impurities and sorted by color.
Glass containers such as bottles and jars are the most commonly recycled form of
glass, and their colors are flint (clear), amber (brown), and green. Other types of glass,
such as window glass, pottery, and cooking utensils, are considered contaminants
because they have different compositions than glass used in containers. The recycled
glass is melted in a furnace and formed into new products.

Glass containers make up 90 percent of the total recycled glass used in the United
States. The recycling rate for glass in 2000 was about 23 percent. Other uses for
recycled glass include glass art and decorative tiles. Cullet mixed with asphalt forms a
paving material called glassphalt.
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Structural Evolution in Mechanically Alloyed Al-Fe Powder Mixtures

The structural evolution in mechanically Debkumar Mukhopadhyay

alloyed binary aluminum-iron powder
mixtures containing 1, 4, 7.3, 10.7, and 25 at.
pct Fe has been investigated using x-ray
diffraction and electron microscopic
techniques. The constitution (number and
identity of phases present), microstructure
(crystal size, particle size) and transformation
behavior of the powders on annealing have
been investigated. The solid solubility of Fe
in Al has been extended up to at least 4.5 at.
pct. compared to the equilibrium value of
0.025 at. pct Fe at room temperature. A fully
amorphous phase plus solid solution in the
Al-10.7 at. pct Fe alloy; agreeing well with
the predictions made using the semi-
empirical Miedema model.
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X-Ray Diffractometry
Amorphous cogel with 3% titanium TS-1 with 3% titanium

TS-1 and VS-1 have a good crystallinity and show the

typical reflexes of the orthorhombic MFI-structure
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Heat flow at heating 10K/min (solid line) and

subsequent cooling with 10K/min