Glass Basics

1. What is Glass?
Following ASTM (US Standard) and DIN (German Standard) definition, glass is an
inorganic product of fusion which has been cooled to a rigid condition without
crystallizing.

Glass is a product obtained by the fusion of several inorganic substances, of which

normally silica (SiO2) in the form of sand is the main one. The fused mass is cooled to
ambient temperature at a rate fast enough to prevent crystallisation, i.e., the molecules
cannot arrange themselves into a crystalline pattern. The fast rate of cooling to prevent
crystallisation applies to transparent glasses, whereas in the case of translucent or opal
glasses, the rate of cooling is such as to produce a pre-determined level of Crystal
formation.

Chart 1: Structure of Glass

2. Types of Glass
A large variety of glass with different chemical and physical properties can be made by a
suitable adjustment to chemical compositions. Glasses vary widely in their chemical make-
up; indeed, there are very few element in the periodic table that have not been incorporated
in a glass of some kind. However, most of the glasses produced commercially on a large
scale may be classified into three main groups: soda-lime, lead and borosilicate, of which
the first is by far the most common.

2.1 Commercial Glasses

The main constituent of practically all commercial glasses is sand. Sand by itself can be
fused to produce glass but the temperature at which this can be achieved is about 1700°C.
Adding other chemicals to sand can considerably reduce the temperature of fusion. The
addition of sodium carbonate (Na2CO3), known as soda ash, in a quantity to produce a
fused mixture of 75% silica (SiO2) and 25% of sodium oxide (Na2O), will reduce the
temperature of fusion to about 800°C. However, a glass of this composition is water soluble
and is known as water glass. In order to give the glass stability, other chemicals like
calcium oxide (CaO) and magnesium oxide (MgO) are needed. The raw materials used for
introducing CaO and MgO are their carbonates CaCO3 (limestone) and MgCO3 (dolomite),
which when subjected to high temperatures give off carbon dioxide leaving the oxides in
the glass.

Most commercial glasses whether for containers, i.e. bottles and jars, flat glass for windows
or for drinking glasses, have somewhat similar chemical compositions of:

70% – 74% SiO2 (silica)

12% – 16% Na2O (sodium oxide)
5% – 11% CaO (calcium oxide)
1% – 3% MgO (magnesium oxide)
1% – 3% Al2O3 (aluminium oxide)

Chart 2: Composition of Soda-Lime Glass

Within these very wide limits the composition is varied to suit a particular products and
production method. The raw materials are carefully weighed and thoroughly mixed, as
consistency of composition is of utmost importance. To the mixture of chemicals a further
raw materials added – broken glass, called cullet. Cullet can come from factory rejects, it
can be collected by the public in Bottle Banks or from the bottling industry. Almost any
proportion of cullet can be added to the mix (known as batch), provided it is in the right
condition, and green glass made from batch containing 95% of cullet is by no means
uncommon. Although the glass collected by Bottle Banks may come from several
manufacturer, it can be used by one of them, as container glass compositions have been
harmonised to make this possible. It is, however, important that glass colours are not mixed
and that the cullet is free from impurities, especially metals and ceramics.

Flat glass is similar in composition to container glass except that it contains a higher
proportion of magnesium oxide.

Soda-lime glasses
These are the most common commercial glasses and have been described. The chemical
and physical properties of soda-lime glasses make them suitable for a visible light and
hence applications. The nominally colourless types transmit a very high percentage of
visible light and hence have been used for windows since at least the time of the Romans.
Soda-lime glass containers are virtually inert, and so cannot contaminate the contents inside
or affect the taste. Their resistance to chemical attack from aqueous solutions is good
enough to withstand repeated boiling (as in the case of preserving jars) without any
significant changes in the glass surface.
One of the main disadvantages of soda-lime is their relatively high thermal expansion.
Silica does not expand very greatly when heated but the addition of soda has a dramatic
effect in increasing the expansion rate and, in general, the higher the soda content of a
glass, the poorer will be its resistance to sudden changes of temperature (thermal shock).
Thus, care is needed when soda-lime containers are filled with hot liquids to prevent
breakages due to rapid thermal expansion.

Lead glasses
The use of lead oxide instead of calcium oxide, and of potassium oxide instead of all or
most of the sodium oxide, gives the type of glass commonly known as lead crystal. The
traditional English full lead crystal contains at least 30% lead oxide (PbO) but any glass
containing at least 24% PbO can be legitimately described as lead crystal according to the
relevant EEC directive. Glasses of the same type, but containing less than 24% PbO, are
known simply as crystal glasses, some or all of the lead being replaced in these
compositions by varying amounts of the oxides of barium, zinc and potassium. Lead
glasses have a high refractive index and relatively soft surface so that they are easy to
decorate by grinding, cutting, engraving. The overall effect of cut crystal is the brilliance of
the two.

Glasses with even higher lead oxide contents (typically 65%) may be used as radiation
shielding glasses because f the well-known ability of lead to absorb gamma rays and other
forms of harmful radiation.

Borosilicate glasses
As the name implies, borosilicate glasses, the third major group, are composed mainly of
silica (70-80%) and boric oxide (7-13%) with smaller amounts of the alkalis (sodium and
potassium oxides) and aluminium oxide. They are characterised by the relatively low alkali
content and consequently have good chemical durability and thermal shock resistance. Thus
they are permanently suitable for process plants in the chemical industry, for laboratory
apparatus, for ampoules and other pharmaceutical containers, for various high intensity
lighting applications and as glass fibres for textile and plastic reinforcement. In the home
they are familiar in the form of ovenware and other heat-resisting ware, possibly better
known under the trade name of the first glass of this type to be placed on the consumer
market- Pyrex.

2.2 Other types of glasses

Special glasses
Glasses with specific properties may be devised to meet almost any imaginable
requirement, the main restriction normally being the commercial considerations, i.e.,
whether the potential market is large enough to justify the development and manufacturing
costs. For many specialised applications in chemistry, pharmacy, the electrical and
electronics industries, optics, the construction and lighting industries, glass, or the
comparatively new family of materials known as glass ceramics, may be the only practical
material for the engineer to use.

Vitreous silica
As mentioned previously, silica glass or vitreous silica is of considerable technical
importance. However, the fact that temperature above 1500°C are necessary in the melting
makes the transparent variety (often known as fused quartz or quartz glass) expensive and
difficult to produce. The less expensive alternative for many applications is fused silica,
which is melted at somewhat lower temperatures; in this case small gas bubbles remain in
the final product which is therefore not transparent.

Another substitute for vitreous silica can be produced by melting a suitable borosilicate
glass and then heating it at around 600°C until it separates into two phases. The alkali-
borate phase may be leached out with acids, leaving a 96% silica phase with open pores of
controllable size which can be converted into clear glass. Porous glasses of this kind,
commonly known as Vycor, from the first commercial version produced by Corning Glass
Works Ltd, may be used as membranes for filtration purposes and for certain biological
applications.

Aluminosilicate glasses
A small, but important group of glasses is that known as aluminosilicate, containing some
20% aluminium oxide (Al2O3) often including calcium oxide, magnesium oxide and boric
oxide in relatively small amounts, but with only very small amounts of soda or potash.
They tend to require higher melting temperatures than borosilicate glasses and are difficult
to work, but have the merit of being able to withstand high temperatures and having good
resistance to thermal shock. Typical applications include combustion tubes, gauge glasses
for high pressure steam boilers, and in halogen-tungsten lamps capable of operating at
temperature as high as 750°C.

Alkali-barium silicate glasses

In normal operation, a television produces X-rays which need to be absorbed by the various
glass components. This protection is afforded by glasses with minimum amounts of heavy
oxides (lead, barium or strontium). Lead glasses are commonly used for the funnel and
neck of the tube, while glasses containing barium are usually employed for the face or
panel.

Borate glasses
There is a range of glasses, containing little or no silica, that can be used for soldering
glasses, metals or ceramics at relatively low temperatures. When used to solder other
glasses, the solder glass needs to be fluid at temperatures (450°C – 550°C) well below that
at which the glass to be sealed will deform.

Some solder glasses do not crystallise or denitrify during the soldering process and thus the
mating surfaces can be reset or separated; these are usually lead borate glasses containing
60-90% PbO with relatively small amounts of silica and alumina to improve the chemical
durability. Another group consists of glasses that are converted partly into crystalline
materials when the soldering temperature is reached, in which case the joints can be
separated only by dissolving the layer of solder by chemical means. Such denitrifying
solder glasses are characterised by continuing up to about 25% zinc oxide.

Glasses of a slightly different composition (zinc-silicoborate glasses) may also be used for
protecting silicon semi-conductor components against chemical attack and mechanical
damage. Such glasses must contain no alkalis (which can influence the semi-conducting
properties of the silicon) and should be compatible with silicon in terms of thermal
expansion. These materials, known as passivation glasses, have assumed considerable
importance with the progress made in microelectronics technology in recent years that has
made the concept of the “silicon chip” familiar to all.

Phosphate glasses
Most types of glass are good insulators at room temperature, although those with a
substantial alkali content may well be good conductors in the molten state. This is because
the conductivity depends mainly on the ability of the alkali ions in the glass to migrate in an
electric field. However, some glasses that do not contain alkalis conduct electrons which
jump from one ion to another. These are known as semi-conducing oxide glasses and are
used particularly in the construction of secondary electron multipliers. Typically they
consist of mixtures of vanadium pentoxide (V2O5) and phosphorous pentoxide (P2O5).

Chalcogenide glasses
Similar semi conductor effects are also characteristic of a series of glasses which can be
made without the presence of oxygen (non-oxide glasses). These may be composed of one
or more elements of the sulphur group in the Periodic Table (called chalcogens, from the
Greek word for sulphur) combined with arsenic, antimony, germanium and/or the halide
(fluorine, chlorine, bromine, iodine). Some of them have potential use as infra-red
transmitting materials and as switching devices in computer memories because their
conductivity changes abruptly when particular threshold voltage values are exceeded, but
most have extremely low softening points and much poorer chemical durability than more
conventional glasses.

Glass Ceramics
An essential feature of glass structure is that it does not contain crystals. However, by
deliberately stimulating crystal growth in appropriate glasses it is possible to produce a
range of materials with a controlled amount of crystallisation so that they can combine
many of the best features of ceramics and glass. Some of these “glass ceramics” formed
typically from lithium aluminosilicate glasses, are extremely resistant to thermal stock and
have found several applications where this property if important, including cooker hobs,
cooking ware, windows for gas or coal fires, mirror substrates for astronomical telescopes
and missile nose cones.

Some special applications of glass

Different forms and varieties of glass are used in almost every conceivable aspect of human
life. Architecture, food and drink, laboratory equipment, instrumentation, the chemical,
nuclear and electrical industries, lighting, optics – the list is endless. For some areas of
application, one type of glass predominates: for example, soda-lime glass is used almost
universally in the building and packaging industries while borosilicate tends to be standard
in the chemical processing industry. However, for some purposes a wide range of glasses is
required to meet different requirements, as is the case with optical glass, glasses for sealing
to metals and glass fibres.

Optical glasses
Glasses can be designed to meet almost any specified combination of optical properties of
which the most important are the refractive index (representing the deviation of a ray of
light striking the glass at an oblique angle) and the dispersion (the dependence of the
refractive index on wavelength).

Glasses with high dispersion relative to refractive index are called flint glasses while those
with relatively low dispersions are called crown glasses. Typically flint glasses are lead-
alkali-silicate compositions whereas crown glasses are soda-lime glasses.

The substitution of other oxides permits considerable variations to be achieved. Thus

barium crown (barium borosilicate), barium flint (barium lead silicate), borosilicate crown
(sodium borosilicate) and crown flint (calcium lead-silicate) are all widely used.
Phosphorous and the rare earths, especially lanthanum, may also be valuable ingredients in
some optical glass compositions. The inclusion of transition elements (copper, titanium,
vanadium, chromium, manganese, iron, cobalt or nickel) in glass produces strong
absorption bands in the ultra violet part of the spectrum as well as broad bands in the
visible and infra-red, enabling a series of colour filters and glasses with modified
transmission properties in the ultra-violet and infra-red to be produced.

The use of rare earth’s has less effect on colour but it is of particular significance in the
manufacture of laser glasses, most of which contain neodymium. The neodymium ions in
the glass, when stimulated, emit radiation at a particular wavelength (1.06um) and this is
transformed into high-intensity coherent optical data, and for various measurement
functions in industry.
A characteristic of some optical glasses is that when they are exposed to ultraviolet or
short-wave infra-red radiation (as with sunlight) they become dark, but when removed from
such exposure they revert to their original state. These, known as photochromic glasses,
include in their composition silver halide crystals produced by adding silver salts and
compounds of fluoride, chlorine or bromine (the halides) to the base-glass (normally
borosilicate). Controlled thermal treatment during and after melting causes extremely small
phase separations to occur and these are responsible for the reversible darkening effect.

Sealing glasses
Another application for which a large variety of glass compositions is used is sealing to
metals for electrical and electronic components. Here the available glasses may be grouped
according to their thermal expansion which must be matched with the thermal expansions
of the respective metals so that sealing is possible without excessive strain being induced
by the expansion differences.

For sealing to tungsten, in making incandescent and discharge lamps, borosilicate alkaline
earths-aluminous silicate glasses are suitable. Sodium borosilicate glasses may be used for
sealing to molybdenum and the iron-nickel-cobalt (Fernico) alloys are frequently employed
as a substitute, the amount of sodium oxide permissible depending on the degree of
electrical resistance required. With glasses designed to seal to Kovar alloy, relatively high
contents of boric oxide (approximately 20%) are needed to keep the transformation
temperature low and usually the preferred alkali is potassium oxide so as to ensure high
electrical insulation.

Where the requirement for electrical insulation is paramount, as in many types of vacuum
tube and for the encapsulation of diodes, a variety of lead glasses (typical containing
between 30% and 60% lead oxide) can be used.

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Glass Properties
Every type of glass has the properties necessary for its intended purpose, e.g. an optical
glass has a particular refraction and an appliance glass has a particular chemical resistance.
However, the properties of a glass, especially its viscosity, play a crucial part in production
or moulding in particular.

These properties are continuously monitored in every operation, and a large quantity of
equipment is required for this. On the basis of the glass composition, it is possible to
calculate some of the properties of the glass.

The following explains in detail some of the parameters that will be calculated in the
analysis:
Viscosity
Viscosity is the most important property, since it is of the greatest significance for the
manufacturing and processing of glass. Viscosity is a temperature-dependent parameter
which is determined by the mobility of the structural particles of the substance in question.
The forces to be overcome with this type of movement of particles are frictional forces.
Viscosity is therefore also described as inner friction.

The movement of individual particles or components is made possible by the tearing apart
of bonds. The energies necessary for this are applied in the melting process through thermal
energies. If the temperature is increased all the time, the number of torn bonds increases
and the viscosity is reduced. As the melt cools down, the bonds close again, which
increases the viscosity.

The (dynamic) viscosity is designated using the symbol 'eta' and represents the force that is
necessary to displace two parallel surfaces at a particular distance at a particular speed. If
the viscosity is related to density, we talk about the kinematic viscosity. However, it is
essential for glass production and glass processing to have corresponding reference or fixed
points for the entire temperature and viscosity range applied during glass manufacture. It is
impossible to manage without these.

These defined fixed points are derived from particular stages in the glass production and are
used primarily for determining the viscosity values of the glass that are most favourable for
these production stages.

In addition, there are empirically determined key figures which are used in practice, since
these affect the setting of the production machinery. Since the viscosity of the glass
changes by more than 13 decimal powers, the logarithm of the viscosity must be plotted as
a function of the temperature.

If the viscosity curve runs steeply from 103 to 106 dPa s, the temperatures for the
corresponding viscosities are relatively close to each other, i.e. the temperature range for
processing the glass is short. Glass manufacturers refer to a glass of this type as being
'short', with the opposite type of glass being 'long'. The size of this temperature range is
described as the length of the glass.

Glass formation
When the batch is heated, the batch components go through a series of interconnected
individual processes which are both technical/physical and chemical in nature which affect
glass formation. These reactions can be divided up as follows:

 Solid body reactions in the area of the grain contacts (silicate formation, CO2
development)
 Formation of carbonatic melts which encase the quartz grains
 Decomposition reactions which create bubbles (CO2...)
  Dissolution reactions of the carbonatic melts with quartz grains (formation of silicate
melts)

The temperature rises constantly. Under the temperature conditions of the batch melting,
these reactions take place more or less at the same time. The formation silicate melts is
completed for Na2O-CaO-SiO2 glasses at approx. .1000°C, for PbO-SiO2 glasses at
approx. 800°C and for Na2O-B2O3-SiO2 glasses at approx. 1.100°C.

A further temperature increase in the melt is necessary, however, in order to achieve good
homogenisation and refining of the glass in a reasonable time.

Relative Machine Speed RMS

The RMS is used in the production of certain container glasses and compares glasses with
the above glass as regards their production behaviour.

Working Range Index

If the Working Range Index (WRI and Devitrification Index) >160, this characterises a low
devitrification index; if it is <160, devitrification is more probable. The Devitrification
Index was introduced for this reason: If D is positive, devitrification is improbable, if D is
negative, devitrification is more likely.

Gob Temperature
The Gob Temperature is the temperature at which the glass has a viscosity of approx. 1000
dPa s. At this temperature, an optimum gob forms. Most machine operators prefer values
<1200 °C.

Density
For the practical application of glass as a consumer object, the density is not particularly
important. What is more interesting is the fact that the density is used as a calculation value
for further properties and that density measurements can be used in practice to carry out, in
a simple way, monitoring of the constancy of the glass composition.

Glasses with a high density are generally glasses with a high lead oxide content, which
particularly includes optical glasses.

Because the density depends on volume, there are differences as regards the heating history
of glasses. A tensioned glass (mainly tensile stress in this case) undergoes an expansion
which causes an increase in volume. The density of a tensioned glass is thus approx. 0.02
less than that of a destressed glass.
Considerable significance is assigned to density in combination with temperature, since it
has a direct effect on glass flows in glass melting furnaces and furnaces.

The density decreases as the temperature rises, which is due to the fact that the cohesion of
the individual components of the glasses is considerable reduced, so that thermal vibrations
start which means that the volume expands.

Specific heat
Glass manufacture is a very heat-intensive process, which means that the thermal
properties, especially specific heat, are very important.

The "true" specific heat at constant pressure is defined as a change in the enthalpy (heat
retention) H with the temperature T

In practically all calculations, however, we are interested in what is called the "average"
specific heat capacity tp_m (at constant pressure), which is determined between two
temperatures T1 (mostly 0°C or 20°C) and T2:

The "true" specific heat can also be determined from this equation

Optical properties
For optical glasses, certain key figures are important for evaluation of the individual glass
types as regards their use in optical systems and in their calculation.

If a ray of light from air in which it has almost the maximum speed of c_0 hits a glass, it
reduces its speed to c as a result of the interplay of the light with the ions making up the
glass. If the light falls vertically, the course of the light does not change; but if it falls at an
angle, a deflection occurs which is covered by the law of refraction; here, alpha or beta
represents the angles of the ray of light in relation to the normal in air or in the glass and n
is the refraction index of the glass.

The main refraction index given is the refraction index ne, or sometimes the refraction index
nd.

The refraction index depends on the wavelength of the light, the temperature and the
pressure. It is therefore usual to give the value for n for 20°C and 1013.25 mbar. The
wavelength for which a refraction index applies is attached as a letter index to the n. In
technical optics, 13 refraction indices are applied for all sorts of different wavelengths of
the spectrum.

Dispersion of light is closely associated with the light refraction. In the language of
technical optics, dispersion is understood to mean the difference in the refraction indices of
a medium for light of various wavelengths. The difference n_f-n_c is described as the
average dispersion d.

The relative dispersion is described by the ratio (n_f-n_c)/(n_d-1). The reciprocal relative
density is described as the Abbe coefficient ny_d.

Apart from the major significance that light refraction and dispersion have for optical
glasses, these properties are also interesting for the commercial glass industry, especially
for lead glasses. High refraction values increase the shine of these glasses, which finally
improves quality effectively.

For practical production, regular measurements of the refraction value can provide a
relatively simple, sufficiently precise check on the consistency of the glass composition,
since even minor deviations will lead to changes in the refractive value.

Surface tension
The surface tension of glass is important during the glass melt and in several stages of
manufacture. A particular within a body is attracted by all the neighbouring particles so that
the resultant force is zero. If, on the other hand, a particle is on the surface, then there are
no forces of attraction on one side and a force in the direction of the interior is created.

In order to take a particle from the inside to the surface, a certain degree of work is
required. Bodies with a large surface therefore have more energy and are attempting to take
on a state of less energy by reducing their surface area. Liquids therefore take on a
spherical shape if possible, since the ratio of surface to volume is lowest in this form.

The enlargement of a surface assumes that particles will be transported from the inside to
the surface, which requires an expenditure of energy. The energy that is required to form a
new surface is described as specific free surface energy. Generally, the designation surface
tension sigma is commoner.

Thermal expansion
The thermal expansion of glass is of major practical significance, especially as regards the
lasting, break-proof melting of various glasses with each other and with other substances. A
precise knowledge of the progress of the thermal expansion of glasses is therefore an
essential precondition for controlling some of the technological processes in glass
production and processing.

The increase in volume of a body through thermal expansion happens on all sides. All
isotropic bodies, including glass, expand at the same time in all directions to the same
extent. This thermal expansion of the glass is caused by the fact that, as the temperature
increases, the thermal energy present in the glass increases and, consequently, the particles
begin to vibrate more. Atoms linked with each other by forces thus spread further apart,
causing expansion.

Thermal expansion is designated by the average longitudinal expansion coefficient

(coefficient of linear expansion) alpha . It is the fraction of the length by which a bar of the
material in question increases in length following a temperature increase of 1 degree:

For the commonest substances, within the temperature limits that are technically
interesting, the a value does not change. This means that the change in length is proportion
to the change in temperature. However, the change in length in the case of glass is not
exactly proportional to temperature, and the coefficient of thermal expansion is therefore
temperature-dependent. In practice, the average coefficient of volume expansion (cubic
expansion coefficient) beta is now used.

Thermal conductivity
The thermal conductivity of glass is very low in comparison with other materials such as
copper, aluminium and iron. It is therefore only important for particular areas of
application.

Heat can be transported in glass through thermal conductivity and thermal radiation. At low
temperatures the first process predominates, with the second occurring more at higher
temperatures.

According to the following definition equation, the thermal conductivity lambda is the
quantity of heat dQ, which flows in the time dt vertically through the surface F at a
temperature there of dT/dx.

In measurements, we generally obtain a total effective thermal conductivity which is made

up of the figures for pure thermal conductivity and thermal radiation. Often, eff l is
described as thermal conductivity for greater simplicity.
Because of the poor thermal conductivity of glass, certain products such as glass fibre
matting, fibreglass and foam glass are used as insulation materials for all sorts of different
applications. The thermal conductivity of foam glass is only approx. 1/20 of that of normal
glass.

Elastic properties
A solid body suffers deformation as a result of a deforming force. If this deformation goes
back completely after the force is removed, the body is described as being ideally elastic.
Hooke's law states that the deformation D is proportional to the stress S applied.

The proportionality constant M occurring in this equation is generally described as a

modulus. Depending on the nature of the deformation, there are various moduli. Their
values depend on the composition; the moduli therefore represent material constants.

Tensile stress creates an expansion which is designated as the modulus of expansion (or the
modulus of elasticity) E. A shearing stress causes shearing strain. The corresponding
modulus G has a number of designations: the modulus of rigidity, shear modulus, twist
modulus, torsion modulus. Finally, pressure on all sides causes compression, with the
modulus of compression K.

With expansion, a transverse contraction occurs in the direction at right angles to this. If the
relative expansion is dl/l and the relative transverse contraction is dd/d, then the ratio is
described as the reciprocal of Poisson ratio

It can be deduced that the reciprocal of Poisson ratio my must lie between 0 and 0.5, A low
reciprocal of Poisson ratio means that with a particular longitudinal expansion there is only
a small transverse contraction.

Electrical properties
The use of glass in electrical engineering has increased considerably in recent years. Here,
it is particularly the electrical properties at normal temperatures that are important, whilst
for electrical glass melting the properties at higher temperatures are important.

Glass is amongst the poorer electrical conductors. Whilst, with good electrical conductors
such as metals, the current is transported via free electrons, conduction is via ions in the
case of glass.

The capacity of a substance to allow the transport of current by freely moving electrons or
ions is described as its electrical conductivity. The electrical conductivity of a material is
dependent on its specific electrical resistance rho.
 The specific electrical conductivity kappa (or sigma) of a material is designated as the
reciprocal value of the specific electrical resistance.

As a consequence of its high rho value, glass is used as an electrical insulating material. As
the temperature increases, the rho decreases, which is due to the fact that the conductive
ions, especially the Na+ ions, become more mobile, thus improving conductivity.

Because kappa, due to the ion conductivity of glass, is also extremely

temperaturedependent, every glass has very different values. At room temperature, a glass
of this type, for example, has a kappa value of 10-13 to 10-14 Ohm-1 cm-1. In the melt
temperature range, kappa increases to 0.1 to 0.3 Ohm-1 cm-1. In practical use, the t_R8
value is often used for operating check measurements. This value is the temperature at
which kappa=100 10-10 Ohm-1 cm-1.

This temperature varies, depending on glass composition, which means that if there is a
change in the measured value, there are likely to be faults in the composition of the glass.
Both parameters, rho and kappa, are material constants which have characteristic values for
glasses of different compositions.

Dielectric properties / permittivity

If a dielectric is placed between the plates of a capacitor, its capacity C increases compared
to the capacity V C measured in a vacuum to

In this equation, the proportionality factor epsilon is described as the permittivity coefficient
epsilon_r or epsilon. The permittivity coefficient is better known as the dielectricity constant
or figure.

The cause of this effect is that displacements of charges occur under the effect of an electric
field. With an ion, the electron sheath can be deformed, or whole ions can be displaced in
their location or can take up completely different positions. The first possibility is all the
more likely, the greater the polarisability of the ion in question is. This means that there is a
correlation with the refraction index for which a corresponding effect is decisive. For very
high frequencies, the Maxwellian ratio applies with the refraction index n:  =n2 which is,
however, not quite met for glass.

If a glass is inserted between the plates of a capacitor, not only is the capacity increased,
but there is also a displacement of the phase angle between current and voltage. As the
current passes through, the glass uses some electrical energy . the dielectrical losses. They
become apparent in that the phase angle around the small angle theta becomes smaller than
90°C.

The quantitative dimension for this energy consumption is the tangent of this angle
tan(theta), which is also described as the loss factor and which is equal to the proportion of
effective power to idle power.

Strength
The tensile strength is one of the most important of the mechanical properties of glass. It
has a major effect on the limit of usability of the glass as regards all sorts of mechanical
stresses and also determines the temperature change resistance (TCR) to a large extent.

The tensile strength is determined by the force F which tears a glass rod with the cross-
section A.

A F z s = The tensile strength is determined by the force F which tears a glass rod with the
cross-section A.

In comparison to other materials such as steel or cast steel, glass has a low tensile strength.
The tensile strength of glass calculated theoretically from the bonding forces gives a value
that is almost a hundred times the practical measurement results. This is due mainly to the
structural micro-cracks and loose areas which also cover the glass surface as notchshaped
unevennesses.

The high risk of fracture of glass following blows and impacts is due to the insufficient
tensile strength. If a glass surface is exposed to blows and impacts, it suffers indentations
which lead to an enlargement and expansion of the surface, causing tensile stress. With
most glasses, even light impacts are enough to exceed the elasticity limit, which leads to an
immediate fracture.

The tensile strength is determined by the force F which tears a glass rod with the cross-
section A.

As a result of the relatively good D s values, glass can be used as a building material in the
form of glass bricks and similar.

Glass is relatively insensitive to compressive stress, and this property is used in practice by
glass having high compressive stresses which considerably improves the tensile strength.
These stresses are created by rapid cooling of the surfaces, especially of flat glasses,
producing safety glass and prestressed glass products.
With these special glass products, these technological treatments considerably increase
impact resistance.

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Batch
combustion de gas con captura de co2
mediante transportadores solidos de oxigebo
basados en cuo
In this module, you can manage all your batch formulae. The raw materials required for
glass production are weighed out in certain quantities in accordance with the glass
composition and mixed with each other. A batch is therefore understood to be the weighed
out ratio of the raw material quantities in the mixed state that is necessary for the
production of a glass with a particular composition.

The term batch formula is understood to mean the defined weight of a particular quantity of
glass containing the individual components calculated for a previously defined total
quantity.

This module offers 2 very interesting calculation possibilities:

You can convert an existing batch to any value you require (the cullet content remains
constant). You can have an existing batch formula automatically converted in such a way
that the resultant glass batch precisely (taking tolerances into account) meets your
requirements (Desired Glass).

Target/actual comparison – glass oxides

As a rule, the calculation of a batch formulae is carried out on the basis of a Desired Glass.
The table “Target/actual comparison – glass oxides” shows you whether the required oxide
proportions in the Desired Glass have been achieved or not.

The column “Oxide” lists all the oxides contained in the batch formula. Alongside these are
the proportions determined in percent. The column “Proportion in Desired Glass” contains
the oxide proportions in the Desired Glass used and the fundamental tolerances. For the
entries in the table that are marked in colour, the oxide proportions in the Desired Glass do
not match the calculated values. In the case of deviations downwards (see arrow), you may
need to add additional raw materials to the batch formula.

Evaporation rates
Any number of different evaporation rates can be set. In this way, particular evaporation
rates can be selected for each batch formula, each furnace or each glass colour. The
following oxides or compounds evaporate in solid form (dust):

SiO2, B2O3 and P2O5, Na2O, K2O, Li2O and Rb2O, TiO2, ZrO2 and SnO2, CaO, MgO,
BaO, PbO, SrO, ZnO, CdO, BeO, FeO, MnO, CuO, CoO and NiO, Al2O3, Fe2O3, Cr2O3,
As2O3, Sb2O3, Bi2O3 and Ga2O3, As2O5 and Sb2O5, Mn3O4

The anions evaporate in gaseous form from the melt and convert accordingly: SO3…SO2,
Cl…HCl, F…HF

The exhaust gas can thus be made up of the following components: CO2, H2O, N2, NO,
NO2, SO2, HCl and HF

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Energy & Mass Balances

With the experience on a large variety of furnaces it is possible to forecast possible
variations mainly focusing on the fuel consumption, such as:

 Electricity vs. Fuel as well as fuel changes

 Batch and/or glass changes or Heat recovery modifications
 Production increase (with additional electricity or oxygen)
 Conversion from air fuel to oxy fuel combustion (or vice versa)
 Recuperator or regenerator repairs

All these forecasts are based on heat and mass balances according to the most common
enunciation of the first law of thermodynamics, that the increase in the internal energy of a
thermodynamic system is equal to the amount of heat energy added to the system minus the
work done by the system on the surroundings. The overall heat and mass balance of any
glass melting furnace can be described as
The accuracy of the forecast is much depending on the base case and the type of variation
or forecast respectively, where the base case can be an existing furnace with given data or
even a new furnace design with only assumptions.

Based on an existing furnace, knowing all input variables, a forecast is very accurate. The
fundamental idea behind is that with the given parameters the overall losses, as described
above, can be calculated very quickly without evaluating the furnace refractory conditions
etc. in detail. Within a specific forecast these losses will not change significantly. Even
when the given parameters are not 100% correct, the forecast or trend respectively will be
very accurate anyhow.

Cullet Ratio
It is well known that increasing the cullet ratio reduces the amount of energy required
significantly. Assuming a furnace for 300 t/d of typical container glass, per 10% of cullet,
the energy consumption can be reduced by about 4-5%.

Cullet Preheating
One way to reduce the energy consumption is to introduce cullet and/or batch preheating.
Assuming the same furnace as above with a typical cullet ratio of 60%, per 100 °C, the
energy consumption can be reduced by about 2-3%.

Water content in the batch

Water in the cullet is typically introduced to the batch to prevent from carry over with
typical volumes of 2-3%. Per 1% of water less in the batch, the energy consumption can be
reduced by about 1.5%.
False Air
False air is not wanted, but always involved. False air has a very important influence on the
energy consumption. 1% less oxygen content in the flue gas results in 6.0% of energy
savings.

Local conditions
There is an influence of the local conditions such as altitude, temperature, barometric level
or air humidity of a given production line. The Knowledge of those parameters helps to best
determine the reference / basic case. The better the base case is the better is the forecast.

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Oxygen Enhanced Combustion (OxyFuel)

Motivation for using oxygen
Glass manufacturers are constantly under pressure to enhance production, improve quality
and meet increasingly strict emission regulations. To overcome these challenges, they are
looking for new ways to increase the pull rate, improve product quality and, in some
instances, extend furnace life (to combat or prevent regenerator plugging).

Oxygen has for many years been successfully used in the glass industry. Different
technologies are available to suit individual furnace and process conditions:

 Oxygen enrichment
 Oxygen lancing
 Oxy-fuel boosting
 All oxy-fuel
Figure 1: Oxygen technologies

All of these processes are based, more or less, on the replacement of air with oxygen.
Thanks to the elimination of nitrogen and the higher concentration of oxygen, they increase
the flame temperature. They also improve the effectiveness of the gas jet due to the higher
concentrations of CO2 and H2O in the vicinity of the flame. These gases are mainly
responsible for thermal radiation.

Oxygen enrichment
Enrichment is the most basic form of using oxygen in glass melting applications.
Enrichment is typically used in a furnace nearing the end of its campaign that is suffering
from regenerator plugging or collapse.

Oxygen lancing
Oxygen lancing is used similarly to enrichment, but is typically associated with more
severe or complex conditions. Lancing is the precise injection of oxygen to the point where
it is most needed. Whilst enrichment is indiscriminate in its injection and is less efficient,
more total oxygen may be injected through lancing.
Oxygen boosting (“Oxy Boosting”)
The difference between boosting and enrichment/lancing is that, in addition to the injection
of oxidant, there is also the addition of fuel. Whilst boosting technologies can be used for
recovery and furnace life extension, they also seek to increase the furnace throughput
and/or improve quality.

The following technologies are examples of boosting.

 Hot spot boosting

 Conventional (horizontal) zero port boost technology
 CGM™ (vertical) Boost Technology

Chart 2 shows a flame view of a vertical crown burner, CGM™.

Figure 2: CGM™ flame view

All oxy-fuel fired melting (“All Oxy Fuel” or “AOF”)

One of the most popular oxygen applications, all oxy-fuel-fired melting eliminates the need
for a combustion air or heat-recovery device. This process is one of the most efficient ways
of reducing nitrogen oxides (NOx) and particulate emissions from glass furnaces.

Figure 3: Energy consumption of air fuel and oxy fuel installations as a function of the flue
gas and air preheating temperatures

Chart 3 shows the energy consumption of different air fuel and oxy fuel installations as a
function of the flue gas and air preheating temperatures i.e. a furnace with a flue gas
temperature of 1480 °C and an air preheating temperature of 1000 °C saves 65% (100-35)
of the energy compared to a furnace with no air preheating. When this furnace would be
converted to AOF we can count with another 9% (35-26) compared to the furnace with no
air preheating or 26% compared with the case of air preheating of 1000 °C.

The benefits of using oxygen within AOF are in particular:

 Reduced emissions with very low NOx and particulate emissions

 Improved heat transfer with enhanced glass quality
 Lower capital costs, no air preheating necessary, smaller filter unit, smaller furnace
 Increased productivity
 Better control over operations, smaller variations
 Replacement of missing combustion air
 Energy savings

Burner technology
Customers can choose from a big variety of burners. Principally all these burners are based
on the principle, that fuel is shielded (conical) with oxygen, so called ‘tube-in-tube’.
Changing the velocities of each partners allows to adapt the flame shape to the furnace and
melting requirements.

When needed oxygen can be partly injected separately, staging, to increase the flame
lengths.

GGC have many experience using oxygen for many purposes.

[Link]

Computer Fluid Dynamics (CFD)

What is Computational Fluid Dynamics?
A general definition is: Computational fluid dynamics (CFD) is the use of computers and
numerical techniques to solve problems involving fluid flows.

CFD helps to answer detailed questions about glass

making.
Typical problems in the glass industry, ggc is dealing with, are the simulation of the
combustion, the batch melting and the flow of the glass melt inside a glass melting furnace.
ggc is using several commercial software packages to create two or three dimensional
simulations from single flames up to complete glass melting furnaces including fore hearths
and regenerators.
The following picture shows an example of a three dimensional simulation of a side port
air- fired float glass tank boosted by 3 roof mounted burners in the zero port area.
Figure 1: Regenerative side-port Furnace boosted by roof mounted burners

A Short Introduction to CFD

The strategy of CFD is to discretize the continuous problem domain with grid points. This
domain can be three, two or one dimensional, but in industrial application mostly three or
two dimensional problem appears. The next graph shows an example of an one dimensional
problem to explain the principles of CFD.

Figure 2: Strategy of Discretization

In this example (see Figure 2) the continuous problem is discretetized in 4 respectively 6

grid points. In this decretized form a variable is only defined at the grid point. The blue line
indicates the exact solution of the function y = x². The dotes show the solution of the
different discrete grids. Obviously the solution is more accurate with a finer discretization.
But with increasing grid points the effort to get a solution increases too.

Figure 3: 2D example of the finite Volume Method

Transferring this strategy to higher dimensions we will end up for two dimensional cases
with area cells and for 3D cases with a volume grid. The main discretisation methods used
are the Finite-Difference Method, Finite-Volume Method and Finite-Element Method. In
simulations of glass melting furnaces and combustion, we are using the Finite-Volume
Method.

This method is discretising the integral equations directly, so that each grid cell can be seen
as a small control volume (look at Figure 3).

Combustion Modelling
Modelling combustion processes requires modelling of flows, reaction and heat transfer.
This means that equations for the momentum balance, mass balance and heat balance have
to be solved simultaneous. Additionally challenges appears because many physical
phenomenas have to be approximated due to technical reasons with simplified approaches.
These Technical reason are to less computational power, which effects a to high time
consumption or deficient knowledge of the process. Good example are the modelling of
turbulent flows or  the reaction modelling of combustion.

GGC is paying special attention to the turbulence chemistry interaction. Here ggc is using
several own adapted solution like detailed kinetic reaction mechanism for pure Oxygen
combustion or state of the art equilibrium assumptions. The spectrum of simulated fuels
reaches from Natural Gas over Hydrogen to Oil. The Oxygen concentration in the oxidant
varies from 21 to 100 Vol.-%. And GGC is able to model nearly every industrial process.

Glass Furnace Modelling

The modelling of the glass melt is not as complex as modelling the combustion. The glass
is treated as a viscose liquid without any reactions. That means only mass transport and the
heat transfer is simulated. The heat transfer through Radiation can be approximated with
the Rooseland approximation, which introduces effective heat conductivity.

But unfortunately there is also batch in the furnace, and modelling batch is very complex,
due to the dependence of the melting behaviour of the batch on the composition, cullet
content, water content, grain size of Batch and Cullet and on the heat transfer rates. The
effect are not only limited on the flow behaviour, gas releases and the glass forming
temperatures but also the reaction paths change.

ggc models nearly every kind of glass melting furnaces. Most of the studies are done to
show the benefits from ggc’s technology at specific customer furnaces. With the help of
CFD simulations ggc is able to identify the optimal burner position and firing distribution
concerning efficiency and glass quality. The spectrum of modelled furnaces contains Air-
fired, Oxy-fired and combined Air/Oxy-fired furnaces, different fuels, all kind of glass
(clear, all colours, and even ultra clear solar glass) and all kind of products (Container,
Fibre, Float).
The following Picture show some examples from the work done in the last years.

Figure 4: Regenerative end-port furnace

Validation of the CFD modelling

To ensure high quality CFD simulations, every simulation has to be checked in regard to
their reliability. ggc does not only rely on their expert working for long time in the glass
industry, but also uses measurements from testing furnaces and from running glass melting
furnaces.

The close cooperation with test facilities, Universities and skilled skilled workshops allows
to build, test and measure every possible burner design and use the results for improving
the CFD- Modelling

Benefits of CFD
CFD has become a powerful tool in combustion and glass melting over the last year for
many reasons. One is the dramatic increase of computational power. Every year
Workstations with faster CPU and more memory are available at lower costs. But there are
others: The Software is improving concerning the handling and the post processing. The
mathematic for solving the differential equations becomes faster. The physics and the
number of the sub models is improved and more important they are validated against
measurements and where weaknesses are found was improved.

Looking at the advantages it lends itself to differ between basic development of equipment
and developing of technologies.
In the development of equipment, like burners or nozzles CFD allows to gain insight into
the design to optimise. Only parts can be tested and optimized virtually without building
the entire combustion test skids, which reduces the development time and costs.
Furthermore it is possible to identify improper designs before building and risks during
testing prototypes can be reduces. The best way will be designing with CFD and validating
later with experiments.

Is the equipment designed, tested and validated, the critical step of integrating the
equipment into the process must be done. This step is difficult due to the high complexity
of a glass melting furnace. Here CFD is able to answer question about the influences before
the installation. It allows to find the optimal process parameter like firing distribution,
burner location, thermocouple positions and helps to find critical aspects to watch at during
operation. CFD can provide you with information at position, where it is not possible to
measure. And CFD can simulate dangerous condition to investigate the consequences.

Up summing, CFD is a widely used tool in designing, testing and integrating of

Technologies, which reduces the costs, time and risk whereas it gives at the same time
more detailed insight information.

Copies of the validation and case studies are available for glass manufacturers upon
request. Please contact us about having your furnace configuration modelled.

[Link]

Revisión de los Métodos Suplementarios de aportación de Oxígeno para la Fusión de

Vidrio

Aumentando el porcentaje de oxígeno en el aire a partir de su 21% inicial se incrementa

significativamente la temperatura de la llama alcanzada con cualquier combustible. Por
ejemplo, el gas natural quemado en el aire alcanza una temperatura de 1938 °C, mientras
que si se quema en un ambiente con un 23% de O2 llega a los 2004 °C.

Cuanto mayores sean las temperaturas de la llama en el horno para vidrio mejor será la
transferencia térmica a la mezcla de materias primas y al vidrio. Esto se debe a que los tres
mecanismos de transferencia del calor, esto es, la conducción, la convección y la radiación,
dependen de la temperatura de la llama:

Conducción   Q µ (Tf - Tp)

Convección   Q µ (Tf - Tp)
Radiación Q µ (Tf - Tp)

Siendo:

Tf = temperatura de la llama
Tp = temperatura del producto
A las temperaturas de fusión del vidrio, la radiación es el modo predominante de
transferencia térmica. Las velocidades de transferencia térmica de la conducción y la
convección dependen linealmente de la diferencia de temperatura entre la llama y el vidrio,
a diferencia de la transferencia térmica debida a la radiación, que es proporcional a la
diferencia entre la temperatura de la llama y la del vidrio, elevadas cada una a la cuarta
potencia. El oxígeno aumenta la temperatura de la llama, lo cual incrementa
significativamente la radiación, el modo predominante de transferencia térmica. Por lo
tanto, con el enriquecimiento con oxígeno, el producto absorbe más calor, se pierde menos
calor en la salida del gas de combustión y el proceso de combustión es más eficaz.

[Link]