GLASS INDUSTRIES

DEFINITIONS OF GLASS:
1. Physically as a rigid, undercooled liquid having no definite melting point
sufficiently high viscosity (greater than 1013 poises) to prevent crystallization.
2. Chemically as the union of the non-volatile inorganic oxides resulting from
the decomposition and fusing of the alkali and alkaline earth compounds,
sand, and other glass constituents.
3. A completely vitrified product or at least such a product with a relatively small
amount of non-vitreous material in suspension.

HISTORY

The Egyptians were making sham jewels of glass which

6,000 or 5,000 B.C.
were often of fine workmanship and marked beauty.
290 A.D. Window Glass is first mentioned.
1608 First glassworks in America.
1639 First glassworks in Salem, Mass.
1688 Plact glass appeared as a rolled product in France.
End of 19th Century Hand-blown window-glass was invented by the Lubbers.
Fourcault process for drawing a sheet of glass
1914
continuously was developed in Belgium.

RAW MATERIALS USED:

1. Sand
For glass manufacture should be almost pure quartz. Its iron content should
not exceed 0.045 per cent for tableware or 0.015 percent for optical glass, as iron
affects adversely the color of most glass.
2. Soda (Na2O)
Is principally supplied by dense soda ash, Na2CO3. The latter is useful in
oxidizing iron and in accelerating the melting. The important sources for lime, CaO,
are limestone and burnt lime from dolomite, CaCO3·MgCO3 the latter introducing
MgO into the batch.
 3. Feldspars
Have the general formula R2O·Al2O3·6SiO2, where R20 represents Na2O or K20
or a mixture of these two. They have many advantages over most other materials as
a source of aluminum oxide, because they are cheap, pure, and fusible and are
composed entirely of glass-forming oxides.
4. Borax
As a minor ingredient, supplies the glass with both sodium oxide and boric
oxide. There is also a high-index borate glass which has a lower dispersion value and
higher refractive index than any glass previously known.
5. Salt Cake
Long accepted as a minor ingredient of glass, and also other sulfates, such as
ammonium and barium sulfates, are encountered frequently in all types of glass. Salt
cake is said to remove the troublesome scum from tank furnaces.
6. Cullet
Is the crushed glass from imperfect articles, trim or otherwise waste glass. It
facilitates the melting and utilizes a waste. It may be as low as 10 percent of the
charge or as high as 80 percent.
7. Refractory Blocks
Have been developed for the glass industry especially because of the severe
conditions encountered here. Sintered zircon, alumina, mullite, mullite-alumina, and
electrocast zirconia-alumina-silica, alumina, and chrome-alumina are typical of those
for glass tanks.

CHEMICAL REACTIONS:

THE RATIOS OF Na₂O/SiO₂ and CaO/SiO₂ ARE NOT MOLAR RATIOS. THE RATIO MAY
BE OF THE TYPE Na₂O/1.8SiO₂, FOR EXAMPLE. IN AN ORDINARY WINDOW GLASS
THE MOLAR RATIOS ARE APPROXIMATELY 1.5MOL Na₂O, 1 MOL CaO AND 5 MOL
SiO₂. OTHER GLASSES VARY WIDELY.
CLASSES OF GLASSES:

1. FUSED SILICA - also known as vitreous silica, is made by high-temperature

pyrolysis of silicon tetrachloride or by fusion of quartz or pure sand.

2. ALKALI SILICATES – the only two-component glasses of commercial

importance; sand and soda ash are simply melted together to produce them.

3. SODA-LIME GLASS – constitutes 95% of all glass manufactured; used for

containers of all kinds, flat glass, automobile and other windows, tumblers and
tableware.

4. LEAD GLASS – obtained by substituting lead oxide for calcium oxide in the
glass melt; has great importance in optical work because of their high index of
refraction and dispersion.

5. BOROSILICATE GLASS – usually contains 10 to 20% B₂O₃, 80 to 87% silica and

less than 10% Na₂O; has a low expansion coefficient, superior resistant to
shock, excellent chemical stability, and high electrical efficiency.

6. SPECIAL GLASSES – such as colored and coated, opal, translucent, safety,

optical, photochromic glasses, and glass ceramics; have varying compositions
depending upon the final product desired.

7. GLASS FIBERS – produced from special glass compositions that are resistant to
weather conditions; low in silica and alkali.

SPECIAL GLASSES:
1. FUSED SILICA GLASS
2. HIGH SILICA GLASS
3. COLORED AND COATED GLASS
4. SAFETY GLASSES
4.1 LAMINATED SAFETY GLASS
4.2 TEMPERED/STRENGTHENED GLASS
5. FOTOFORM
6. PHOTOCHROMIC SILICATE GLASSES
7. GLASS-CERAMICS
8. FIBERGLASS
MANUFACTURING SEQUENCE:
1. Transportation of Raw Materials to Plant(OP)
2. Sizing of Some Raw Materials(OP)
3. Storage of Raw Materials(OP)
4. Conveying, Weighing and Mixing Raw Materials, and Feeding them into Glass
Furnace(OP)
5. Burning of Fuel to Secure Temperature Needed for Glass Formation(PR)
6. Reactions in Furnace to Form the Glass(PR)
7. Heat Saving by Regeneration or Recuperation(OP)
8. Shaping of Glass Products(OP)
9. Annealing of Glass Products(OP)
10. Finishing of Glass Products(OP)

METHODS OF MANUFACTURE
The manufacturing procedures may be divided into four major phases:
(1) MELTING, (2) SHAPING OR FORMING (3) ANNEALING and (4) FINISHING

1. MELTING
Glass furnaces may be classified as either POT OR TANK FURNACES

 POT FURNACES
Approximate capacity of 2 tons or less. Used advantageously for small
production of special glasses or where it is essential to protect the melting batch
from the products of combustion. They are employed principally in the manufacture
of optical glass, art glass, and plate glass by the casting process.
 TANK FURNACE
 Batch materials are charged into one end of a large "tank" built of refractory
blocks. Some measure 125 by 30 by 5 ft. with a capacity of 1,400 tons of molten
glass. The glass forms a pool in the hearth of the furnace, across which the flames
play alternately from one side or the other. “Fined” glass is worked out of the
opposite end of the tank, the operation being continuous.
*Fining is allowing molten glass sufficient time for the bubbles to rise and
leave or dissolve in glass

The foregoing types are regenerative furnaces

The Regenerative Furnace operates in two cycles with two sets of checker
work chambers. The flame gases, after giving up their heat in passing across the
furnace containing the molten glass, go downward through one set of chambers
stacked with open brickwork or checker work.

2. SHAPING OR FORMING
Glass may be shaped by either machine or hand molding. The
outstanding factor to be considered in machine molding is that the design of
the glass machine should be such that the article is completed in a very few
seconds. During this relatively short time the glass changes from a viscous
liquid to a clear solid. It can, therefore, be readily appreciated that the design
problems to be solved, such as flow of heat, stability of metals, and clearance
of bearings, are very complicated.

 WINDOW GLASS
For many years window glass was made by an extremely arduous hand
process that involved gathering a gob of glass on the end of a blowpipe and
blowing it into a cylinder. The ends of the latter were cut off, the hollow
cylinder split, heated in an oven, and flattened. This tedious manual process
has now been entirely supplanted by two continuous processes or their
modifications, the Fourcault Process and the Colburn Process.

The FOURCAULT PROCESS is a method of manufacturing flat glass.

Fourcault is an example of a “vertical draw” process, in that the glass is drawn
against gravity in an upward direction. First developed in Belgium by Emile
Fourcault during the early 1900s.
 In COLBURN PROCESS, the production of sheet glass began with an iron
rod as “bait” immersed lengthwise in a shallow tank of molten glass. This
caused some glass to stick to the rod, drawing a ribbon of glass horizontally
over a set of rollers which roughly formed a flat sheet of glass as it continued
to be drawn out of the molten reservoir.

 PLATE GLASS
Previous to the First World War, plate glass was manufactured by
pouring the molten charge on a fiat, cast-iron table, just ahead of a heavy cast-
iron, water-cooled roller which rolled the glass into a plate of uniform
thickness. These tables were usually about 16 by 30 ft. and were covered with
fine sand to prevent sticking and chilling. The glass was then pushed into a
series of five annealing ovens. Great skill and careful timing were required to
coordinate the roll speed and rate of pouring so that the glass produced might
be rolled smoothly without seams or folds.

 FLOAT GLASS
Developed by Pilkington Brothers in England. It is a fundamental
improvement in manufacturing high-quality flat glass. It has long been known
that fire-polished glass has superior reflectance and wear qualities. The float
process employs the tank furnace melting system.

 WIRED AND PATTERNED GLASS

In patterned glass manufacture, the molten glass flows over the lip of
the furnace and passes between metal rolls on which a pattern has been
engraved or machined. The rolls form the glass and imprint the pattern in a
single operation. Such glass diffuses the light and ensures a certain amount of
privacy, which recommends it for use in rooms, doors, and shower enclosures.
Such glass can be reinforced with wire during the initial forming for special
safety needs.

 BLOWN GLASS
One of the most ancient arts, until the last century depended
solely upon human lungs for power to form and shape molten glass. The
machine making of bottles is only a casting operation that uses air pressure to
create a hollow. Several types of machines produce parisons, partly formed
bottles or bottle blanks. One is the suction-feed type used, with variations, in
bulb and tumbler production. Another is the gob-feed type, which has been
applied to manufacture of all types of ware made by pressing, blowing or a
combination of both.

 LIGHT GLASS
Blowing of thin bulb differs from bottle manufacture in that the
shape and size of the bulb are determined initially by the air blast itself and
not by the mold. The molten glass flows through an annular opening in the
furnace and down between two water-cooled rollers, one of which has circular
depressions that cause swellings on glass ribbon coinciding with circular holes
on a horizontal chain conveyor onto which the ribbon moves next.

 TELEVISION TUBES
Television tubes are now made as large as 68 cm across and
consist of three principal parts, the face phosphorescent screen, on which the
picture is produced, the envelope, and the electro gun. The phosphor is
applied to the face screen of the envelope either by settling or dusting.
Manufacture of the glass envelope was difficult until centrifugal casting was
invented, which uses revolving mold to produce a much more uniform wall
thickness. Glass parts are sealed together, using a gas flame or gas and
electricity. For colored televisions tubes, the phosphor is applied to the inner
surface of the screen.

 GLASS TUBING
For many years glass tubing has been drawn by hand and, for certain
special tubings, it is still being made in that way. However, most tubing sold
today is produced by machines, using either of two processes: Danner Process
or Vello Process.

In the DANNER PROCESS, glass that has been melted in either a tank or
a pot furnace is transferred to a special pot which feeds into a constant-level
trough or forehearth. This trough is divided into three compartments by
bridges which hold back surface impurities from the molten glass passing
through. The flow is controlled by a gate. The glass escapes over a lip onto the
revolving mandrel in the form of a ribbon. The mandrel is a tube of nickel-
chrome alloy on which is mounted a sleeve of clay or other refractory material.
 In the VELLO PROCESS, molten glass flows into a drawing compartment
from which it drops vertically through an annular space surrounding a rotating
rod or blowpipe in which air pressure is maintained to produce tubing of the
desired diameter and wall thickness.

3. ANNEALING
To reduce strains, it is necessary to anneal all glass objects, whether
formed by machine- or hand-molding methods. Briefly, annealing involves two
operations:
1) Holding a mass of glass above a certain critical temperature long enough to
reduce internal strain by plastic flow to less than a predetermined
maximum
2) Cooling the mass to room temperature slowly enough to hold the strains
below this same maximum. The lehr or annealing oven is nothing more
than a carefully designed heated chamber in which the rate of cooling can
be controlled so as to meet the foregoing requirements.

4. FINISHING
All types of annealed glass must undergo certain finishing operations, which,
though relatively simple, are very important. These include cleaning, grinding,
polishing, cutting, sandblasting, enameling, grading, and gaging. Although all of
these are not required for every glass object, one or more is almost always
necessary.

MANUFACTURE OF SPECIAL GLASSSES

1. FUSED SILICA GLASS

Also known as vitreous silica. May be made by fusing pure silica, but
such products are usually blebby and difficult to produce in transparent form.
Now manufactured by vapor-phase high temperature pyrolysis of silicon
tetrachloride. This type of process lends itself naturally to controls which permit
chemically pure SiO₂. The raw silica produced in this manner is in the form of
plates, or boules. The high temperature of the reaction tends to drive off
undesired contaminants, giving fused-silica impurities.
 2. HIGH-SILICA GLASS
Known as Vycor. Constitutes as an important advance toward the
production of a glass approaching fused silica in composition and properties. The
finished articles contain approximately 96% silica and 3% boric oxide, and the rest
is alumina and alkali. Borosilicate-glass compositions of about 75% silica content
are used in the earlier stages of the process, in which the glasses are melted and
molded. After cooling, the articles are subjected to heat treatment and annealing,
which induce the glass to separate into two distinct physical phases. One phase is
high in boric and alkaline oxides while the other is rich in silica.

3. COLORED AND COATED GLASSES

Colored glass may be one of three types:
(a) Color is produced by absorption of certain light frequencies by agents in
solution in the glass
(b) Color is produced by colloidal particles precipitated within an originally
colorless glass by heat treatment
(c) Color is produced by microscopic or larger particles which may be
colored themselves, such as selenium reds (SeO₂) used in traffic lights,
lantern globes.
While coated glasses are made by depositing transparent metallic films
on the surface of clear or colored glass. The films are designed to provide specific
transmission and reflection characteristics which are important to architecture
today.

4. SAFETY GLASS
May be grouped into two general classes: laminated glass and heat-
strengthened (or tempered) safety glass.

 Laminated Safety Glass

The most widely used, consists of two sheets of thin plate glass,
each of which is about 0.125 in. thick, with a sheet of non-brittle plastic
material between. The manufacturing procedure is somewhat as
follows: The plastic and glass are washed and an adhesive is applied to
the glass. The glass and plastic sheet are pressed together under
moderate heat to seal the edges.
The glass is subjected to high temperatures and hydraulic
pressures in an autoclave, in order to bring the entire interlayer into
 intimate contact, after which the edges of the sandwich may be sealed
with a water-resistant compound.

 Tempered Safety Glass

Considerably more resistant to forces that produce bending and
to objects that do not crack or penetrate the compressional layer, but it
is weaker to the impact of missiles traveling at sufficiently high velocities
to break the compression layer. It is merely a single sheet of glass, heat-
treated so that the outer surface is in a state of compression caused by
cooling. When the outer layer is punctured, it shatters into many small
pieces. Such glass is really strong in compression and very weak in
tension.

5. FOTOFORM
A photosensitive glass that is essentially a lithium silicate
modified by potassium oxide and aluminum oxide and contains traces of
cerium and silver compounds as photosensitive ingredients. Under
exposure to ultraviolet light, nuclei are formed by silver sensitized by the
cerium, around which an image of lithium metasilicate results upon
development by heat treatment to near 600°C.

6. PHOTOCHROMIC SILICATE GLASSES

Supplement fotoform glass but possess the following unusual
properties:
Optical darkening
Optical bleaching or fading in the dark
Thermal bleaching at higher temperatures

7. GLASS-CERAMIC
A material melted and formed as glass, and then converted largely
to a crystalline ceramic by process of controlled devitrification. Ceramics
are usually bodies with crystalline and high melting particles bound
together either in a vitreous matrix or by fusion of particles at their grain
boundaries.
 8. FIBERGLASS
Although not a new product, owes its enhanced usefulness to its
extreme fineness (often about 10 µm but may be down to 5 µm or less). It
can be drawn into thread or blown into a mat for insulation, tape, and air
filters. The drawn fibers are used to reinforce various plastics and the
composite product is fabricated into pipes, tanks, and sporting goods, such
as fishing rods and skis. The most common resins used are epoxies and
polyesters. A special glass, low in silica, is used for production of fibers.

REFERENCES:
SHREVE’S CHEMICAL PROCESS INDUSTRIES (FIFTH EDITION) BY GEORGE T. AUSTIN

PREPARED BY:
HIBALER, MARY ANGELIQUE
REQUIRON, ANGELOU
ME5D