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Pamantasan ng Lungsod ng Maynila

College of Engineering and Technology


Department of Chemical Engineering

Chemical Process Industries

CERAMIC
INDUSTRY

Submitted by:
BS ChE 3 Group 2
Garcia, Ann Clarisse M.
Santos, Amabelle C.
Sison, Bren A.
Torres, Clark Ivan V.

Submitted to:
Engr. Milagros R. Cabangon
Instructor

November 18, 2016

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Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

TABLE OF CONTENTS

Objectives ....................................................................................................... 3
Introduction .................................................................................................... 4
Brief History ................................................................................................... 5
Raw Materials ................................................................................................. 6
Ceramic Tiles .................................................................................................. 7
Types..................................................................................................... 8
Manufacturing Process .......................................................................... 9
Manufacturing Companies ................................................................... 14
Whitewares ................................................................................................... 15
Types................................................................................................... 16
Raw Materials ...................................................................................... 18
Manufacturing Process ........................................................................ 19
Manufacturing Companies ................................................................... 23
Plant Layout ........................................................................................ 24
Process Layout .................................................................................... 24
Structural Clay Products ............................................................................... 25
Raw Materials ...................................................................................... 25
Manufacturing Process ........................................................................ 27
Manufacturing Companies ................................................................... 28
Process Layout .................................................................................... 29
Refractories................................................................................................... 30
Classifications ..................................................................................... 30
Varieties .............................................................................................. 33
Uses and Applications ......................................................................... 36
Manufacturing Companies ................................................................... 39
Manufacturing Process ........................................................................ 40
Specialized Ceramic Product ......................................................................... 47

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Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Ceramic Composites ............................................................................ 47


Ferroelectric and Ferromagnetic Ceramics ........................................... 49
High-Alumina Ceramics ....................................................................... 50
Vitreous Enamel ........................................................................................... 51
Raw Materials ...................................................................................... 51
Manufacture of the Frit ........................................................................ 52
Preparation of Metal Parts ................................................................... 52
Application of the Enamel .................................................................... 53
Firing .................................................................................................. 53
References .................................................................................................... 54

OBJECTIVES

General Objective:
To identify and enumerate the raw materials, unit operations and
equipment involved in the manufacturing process of ceramics.

Specific Objectives:
• To identify the major and minor raw materials in the production of
ceramics.

• To enumerate the different types of industries under ceramics.

• To determine the manufacturing process of tiles, whitewares, bricks,


refractories and specialized ceramics.

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Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

INTRODUCTION

Ceramics comprise all engineering materials that are chemically inorganic,


except metals and alloys and are usually rendered serviceable through high
temperature processing. Ceramics are widely known because of its durability
and flexibility to form different products. It is usually made from clay, feldspar
and silica. Some of the products of the ceramic industry are

 Porcelain Containers
 Whitewares
 Industrial Ceramics
 Pottery
 Refractories

The word ceramics, that was first used in 1890, came from the Greek word
keramikos. The coined term came from the popular keramos potter’s clay.

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Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

BRIEF HISTORY
YEAR DEVELOPMENT
26,000 Early man discovers that the clay or the mud combined with
BC the mammoth fat and bone that is composed of bone ash and
loess is moldable, thus, created the first ceramic art.

6,000 Ceramic firing was first introduced in Ancient Greece. This


BC also started the Greek pottery called pithari. These pots were
used for storage and for burial purposes.

4,000 Glass and ceramic tiles are discovered in Ancient Egypt. It


BC consists of silicate glaze over a sintered quartz body primarily
used for jewelry. The royalties wear these jewelries to declare
their rank in the community.
600 AD Chinese created the first ceramic composite, the porcelain. It
is made by firing clay with feldspar and quartz. This starts the
porcelain industry in the world.

1870’s Refractory materials are introduced during the Industrial


Period. These materials can resist high temperatures since it
is usually made from lime and magnesium oxide.

1889 The American Ceramic Society was founded by Elmer E.


Gorton, Samuel Geijsbeak and Colonel Edward Orton Jr. They
aim to develop and improve the ceramic industry in the world.

1960 A new field called fiber optics opens with the discovery of the
laser and the observation that its light will travel through glass.

1987 Scientists discovered superconducting ceramic oxide. These


ceramic superconductors is applied to integrated circuits of
high speed computers.
1992 Certain ceramics known as “smart materials” are introduced.
This applies to smart sensors that react to variable surface
conditions.

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Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

RAW MATERIALS
Because of the large volumes of product involved, traditional
ceramics tend to be manufactured from naturally occurring raw materials. In
most cases these materials are silicates—that is, compounds based on silica
(SiO2), an oxide form of the element silicon. In fact, so common is the use of
silicate minerals that traditional ceramics are often referred to as silicate
ceramics, and their manufacture is often called the silicate industry. Many of
the silicate materials are actually unmodified or chemically modified
aluminosilicates (alumina [Al2O3] plus silica), although silica is also used in its
pure form. Altogether, the raw materials employed in traditional ceramics fall
into three commonly recognized groups: clay, silica, and feldspar. These groups
are described below.

Clay
Clay minerals such as kaolinite
(Al2[Si2O5][OH]4) are secondary geologic
deposits, having been formed by the weathering
of igneous rocks under the influence of water,
dissolved carbon dioxide, and organic acids. The
largest deposits are believed to have formed
when feldspar (KAlSi3O8) was eroded from rocks
such as granite and was deposited in lake beds,
where it was subsequently transformed into clay.

The importance of clay minerals to traditional ceramic development and


processing cannot be overemphasized. In addition to being the primary source
of aluminosilicates, these minerals have layered crystal structures that result in
plate-shaped particles of extremely small micrometer size. When these particles
are suspended in or mixed with water, the mixture exhibits unusual rheology,
or flow under pressure. This behavior allows for such diverse processing methods
as slip casting and plastic forming, which are described below. Clay minerals are
therefore considered to be formers, allowing the mixed ingredients to be formed
into the desired shape.

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Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Silica
Other constituents of traditional ceramics are
silica and feldspar. Silica is a major ingredient in
refractories and whitewares. It is usually added as
quartz sand, sandstone, or flint pebbles. The role of
silica is that of a filler, used to impart “green” (that is,
unfired) strength to the shaped object and to maintain
that shape during firing. It also improves final
properties.
Feldspar
Feldspars are aluminosilicates that contain
sodium (Na), potassium (K), or calcium (Ca). They range
in composition from NaAlSi3O8 and KAlSi3O8 to
CaAl2Si2O8. Feldspars act as fluxing agents to reduce
the melting temperatures of the aluminosilicate phases.

CERAMIC TILES
Wall and floor tile used for interior and
exterior decoration belongs to a class of ceramics
known as whitewares. The production of tile dates
back to ancient times and peoples, including the
Egyptians, the Babylonians, and the Assyrians.
For instance, the Step Pyramid for the Pharoah
Djoser, built in ancient Egypt around 2600 B.C. ,
contained colorful glazed tile. Later, ceramic tile
was manufactured in virtually every major
European country and in the United States. By
the beginning of the twentieth century, tile was manufactured on an industrial
scale. The invention of the tunnel kiln around 1910 increased the automation of
tile manufacture. Today, tile manufacture is highly automated.

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Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

TYPES OF CERAMIC TILES


In terms of raw materials
1. Red- Body Ceramic Tiles
Tiles made from clay that acquire a
color that ranges from yellow to intense red
brown. It depends on their iron oxide content
and their manganese oxide content.
.
2. White- Body Ceramic Tiles
Tiles made from clay that contain
no coloring oxides in their composition and
acquire a white color.
3. Porous Ceramic Tiles
Dependent on the carbonate
content in the clay composition and on the
forming and firing process.
In terms of forming method
1. Extruded Ceramic Tiles (A)
Tiles obtained from molding in which a plastic paste is pressed
through a die called extruder. The resulting tile have grooves in the back and
then need to be mechanically separated.
2. Pressed Tiles (B)
Tiles made using the forming method based on a clay composition
in powder form and with a low moisture content. Mechanical pressing of this
gives rise to the pressed product.
In terms of glazing application
1. Glazed Tile (GL)
This refers to the ceramic tiles whose fair face is coated by one or
more glazes.

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Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

2. Unglazed Tile (UGL)


This refers to the tiles whose fair face is not coated either wholly or
in part, by any glaze. Examples are terracotta tile and porcelain tile.
MANUFACTURING PROCESS OF TILES

Source: Mariwasa Siam Corporation Philippines


PREPARATION OF RAW MATERIALS
The raw materials must be pulverized and classified according to particle
size. Primary crushers are used to reduce large lumps of material. Either a jaw
crusher or gyratory crusher is used, which operate using a horizontal squeezing
motion between steel plates or rotating motion between steel cones, respectively.

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Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Secondary crushing reduces smaller lumps to particles. Hammer or muller


mills are often used. A muller mill uses steel wheels in a shallow rotating pan,
while a hammer mill uses rapidly moving steel hammers to crush the material.
Roller or cone type crushers can also be used.
A third particle size reduction step may be necessary. Tumbling types of
mills are used in combination with grinding media. One of the most common
types of such mills is the ball mill, which consists of large rotating cylinders
partially filled with spherical grinding media.
Screens are used to separate out particles in a specific size range. They
operate in a sloped position and are vibrated mechanically or
electromechanically to improve material flow. Screens are classified according to
mesh number, which is the number of openings per lineal inch of screen surface.
The higher the mesh number, the smaller the opening size.
Once the raw materials are processed, a number of steps take place to
obtain the finished product. These steps include batching, mixing and grinding,
spray-drying, forming, drying, glazing, and firing. Many of these steps are now
accomplished using automated equipment.

BATCHING
For many ceramic products,
including tile, the body composition is
determined by the amount and type of
raw materials. The raw materials also
determine the color of the tile body,
which can be red or white in color,
depending on the amount of iron-
containing raw materials used.
Therefore, it is important to mix the
right amounts together to achieve the desired properties. Batch calculations are
thus required, which must take into consideration both physical properties and
chemical compositions of the raw materials. Once the appropriate weight of each
raw material is determined, the raw materials must be mixed together.

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

MIXING AND GRINDING


Once the materials are weighed, they are added together into a shell
mixer, ribbon mixer, or intensive mixer. A shell mixer consists of two cylinders
joined into a V, which rotates to tumble and mix the material. A ribbon mixer
uses helical vanes, and an intensive mixer uses

rapidly revolving plows. This step further grinds the ingredients, resulting in a
finer particle size that improves the subsequent forming process (see step #4
below).
Sometimes it is necessary to add water to improve the mixing of a multiple-
ingredient batch as well as to achieve fine grinding. This process is called wet
milling and is often performed using a ball mill. The resulting water-filled mixture
is called a slurry or slip. The water is then removed from the slurry by filter
pressing (which removes 40-50 percent of the moisture), followed by dry milling.

SPRAY DRYING
If wet milling is first used, the
excess water is usually removed via spray
drying. This involves pumping the slurry
to an atomizer consisting of a rapidly
rotating disk or nozzle. Droplets of the slip
are dried as they are heated by a rising hot
air column, forming small, free flowing
granules that result in a powder suitable
for forming.
Tile bodies can also be prepared by dry grinding followed by granulation.
Granulation uses a machine in which the mixture of previously dry-ground

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

material is mixed with water in order to form the particles into granules, which
again form a powder ready for forming.

FORMING
Most tile is formed by dry pressing.
In this method, the free flowing powder—
containing organic binder or a low
percentage of moisture—flows from a
hopper into the forming die. The material
is compressed in a steel cavity by steel
plungers and is then ejected by the
bottom plunger. Automated presses are
used with operating pressures as high as
2,500 tons.
Several other methods are also used
where the tile body is in a wetter, more moldable form. Extrusion plus punching
is used to produce irregularly shaped tile and thinner tile faster and more
economically. This involves compacting a plastic mass in a high-pressure
cylinder and forcing the material to flow out of the cylinder into short slugs.
These slugs are then punched into one or more tiles using hydraulic or
pneumatic punching presses.
DRYING
Ceramic tile usually must be dried (at high relative humidity) after forming,
especially if a wet method is used. Drying, which can take several days, removes
the water at a slow enough rate to prevent shrinkage cracks. Continuous or
tunnel driers are used that are heated using gas or oil, infrared lamps, or
microwave energy. Infrared drying is better suited for thin tile, whereas
microwave drying works better for thicker tile. Another method, impulse drying,
uses pulses of hot air flowing in the transverse direction instead of continuously
in the material flow direction.

GLAZING
A glaze is a glass material designed to melt onto the surface of the tile
during firing, and which then adheres to the tile surface during cooling. Glazes

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

are used to provide moisture resistance and decoration, as they can be colored
or can produce special textures.
To prepare the glaze, similar methods are used as for the tile body. After a batch
formulation is calculated, the raw materials are weighed, mixed and dry or wet
milled. The milled glazes are then applied using one of the many methods
available. In centrifugal glazing or discing, the glaze is fed through a rotating disc
that flings or throws the glaze onto the tile. In the bell/waterfall method, a stream
of glaze falls onto the tile as it passes on a conveyor underneath. Sometimes, the
glaze is simply sprayed on. For multiple glaze applications, screen printing on,
under, or between tile that have been wet glazed is used. In this process, glaze
is forced through a screen by a rubber squeegee or other device.

Dry glazing is also being used. This involves the application of powders, crushed
frits (glass materials), and granulated glazes onto a wet-glazed tile surface. After
firing, the glaze particles melt into each other to produce a surface like granite.

FIRING
After glazing, the tile must be heated intensely to strengthen it and give it
the desired porosity. Two types of ovens, or kilns, are used for firing tile. Wall
tile, or tile that is prepared by dry grinding instead of wet milling), usually
requires a two-step process. In this process, the tile goes through a low-
temperature firing called bisque firing before glazing. This step removes the
volatiles from the material and most or all of the shrinkage. The body and glaze
are then fired together in a process called glost firing. Both firing processes take
place in a tunnel or continuous kiln, which consists of a chamber through which

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

the ware is slowly moved on a conveyor on refractory batts—shelves built of


materials that are resistant to high temperatures—or in containers called
saggers. Firing in a tunnel kiln can take two to three days, with firing
temperatures around 2,372 degrees Fahrenheit (1,300 degrees Celsius).

For tile that only requires a single firing—usually tile that is prepared by wet
milling—roller kilns are generally used. These kilns move the wares on a roller
conveyor and do not require kiln furnitures such as batts or saggers. Firing times
in roller kilns can be as low as 60 minutes, with firing temperatures around
2,102 degrees Fahrenheit (1,150 degrees Celsius) or more.

TILE MANUFACTURING COMPANIES IN THE PHILIPPINES


LEPANTO CERAMICS INCORPORATED
Address: Makiling, Calamba City, Laguna
MARIWASA SIAM CERAMICS INC.
Address: Brgy. San Antonio, Santo Tomas,
Batangas
FORMOSA CERAMIC TILES MFG. CORP.
Address: Quezon Road, Brgy. San Isidro,
San Simon, Pampanga
EUROTILES SUPERIOR CERAMIC TILES
Address: L. Sumulong Memorial Cir. San Jose St., Antipolo, Rizal
KALAYAAN TILES CORPORATION
Address: 51 Kalayaan St. Quezon City,
Metro Manila

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

WHAT ARE WHITEWARES?


Whiteware is a generic term for ceramic
products which are usually white but not
necessarily white and of fine texture. They are
consisted typically of clays, feldspar and potter’s
flint.

Whitewares usually differ in their:

 Vitreous appearance – like glass in appearance or physical properties.


Usually translucent due to the presence of a glass phase.

(vitreous, semi-vitreous, non-vitreous)

 Porous – having minute spaces or holes through which liquid or air may

pass.

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

 Glaze – is an impervious layer or coating of a vitreous substance which

has been fused to a ceramic body through firing. Glaze can serve to color,
decorate or waterproof an item.

TYPES OF WHITEWARE

1. Earthenware
Earthenware is a semi-vitreous dinnerware
which is porous and non-translucent with a
soft laze

2. Chinaware
Chinaware is a vitrified translucent ware
with a medium glaze which resists abrasion
to a degree. It is used for non-technical
purposes.

3. Porcelain
Porcelain is a vitrified translucent ware
with a hard glaze which resists abrasion to
the maximum degree. It includes chemical
insulating and dental porcelain.

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

4. Sanitary ware
Sanitary ware, formerly made from clay, was
usually porous, hence a vitreous
composition is presently used. Prefired and
sized vitreous grog is sometimes included
with the triaxial composition.
5. Stoneware
Stoneware, one of the oldest of ceramic
wares, was in use long before porcelain was
developed. In fact, it may be regarded as
crude porcelain not so carefully fabricated
from raw material of a poorer grade.

6. Whiteware tiles
Whiteware tiles, available in a number of
special types, are generally classified as floor
tiles, which are resistant to abrasion and
impervious to stain penetration and may be
glazed or unglazed, and as wall tiles which also
have a hard, permanent surface and come in a
variety of colors and textures.

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Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

RAW MATERIALS

1. Flint - (SiO2)
It is also known as Silica Sand or Quartz. It
provides an aggregate framework for the
fired matrix. A major raw material in
ceramics and refractories.
2. China Clay - (Al2O3.2SiO2.2H2O)
It is also called as Kaolinite or Kaolin Clay.
Secondary geologic deposits. Primary source of
alumino silicates. Imparts plasticity and drying
hardness to the wet materials and transforms
into a mesh of crystals during firing
3. Feldspar - (K2O.Al2O3.6SiO2)
It acts as the fluxing agent to reduce melting
temperatures of alumino silicate phases.
The melting of the feldspar fills the voids
between the silica and clay particles and
cements them into a strong mass.

 To create different types of porcelain, craftspeople combine these raw


materials in varying proportions until they obtain the desired properties.
 However, the most common ratio used for the production of porcelain is:

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Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

MANUFACTURING PROCESS OF PORCELAIN

There are three methods to produce porcelain:

1. Wet-Process Porcelain
Used for the production of fine-grained, highly glazed insulators for high-
voltage service.
2. Dry- Process Porcelain
Employed for rapid production of more open-textured, low voltage pieces
3. Cast Porcelain
Necessary for the making of pieces which are too large, too intricate or too
detailed for the other two methods.

These three processes are based on the same raw material. The difference
between the processes is in the manufacturing being largely in drying and
forming steps.

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

MANUFACTURING OF WET-PROCESS PORCELAIN

PROCEDURE EQUIPMENT USED

Primary Crushing
- Preliminary crushing of the raw
materials, mainly, feldspar, flint
and china clay.
Equipment Used: Jaw Crusher

Secondary Crushing
- For reduction of particles to 0.1
inch (.25 centimeter) or less in
diameter.
Equipment Used: Hammer Mill

Blunging
- Water is added to the mixture of
raw materials to form a slurry.
Equipment Used: Blunger

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Magnetic Filtration
- is performed to remove iron
from the slurries because iron
occurs so pervasively in most
clays. Iron must be removed
because it will leave a reddish
hue when it oxidizes.
Equipment Used: Magnetic Separator

Pressing
- Water is removed from the
slurry to produce a clay mass.
Equipment Used: Filter Press

De-airing
- All the air is taken out to
produce a denser, more uniform
and stronger porcelain.
Equipment Used: Vacuum Pug Mill

Jiggering
- it is a term used for
mechanical way of forming of
clay mass into different molds.
Equipment Used: Jiggering Machine

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Drying
- The molded clay is preliminarily
dried, trimmed before glazing.
- They are heated at a relatively
low temperature
Equipment Used: Tunnel Dryer
Glazing
- The procedure to add gloss to the porcelain.
- Applied to the ware by means of painting, spraying, dipping or pouring.
- Usually contains alumina, silica and calcia
Vitrification
- The heart of the process which
will heat the glazed wares into
a 1500 degrees Celsius.
- The formation of glass,
accomplished in this case
through the melting of
crystalline silicate compounds
into the amorphous,
noncrystalline atomic structure
associated with glass.
Equipment Used: Tunnel Kiln or
Electric Kiln
Decorating and Packaging
- Designing the surface of the porcelain. This process is optional since
not all of the porcelain products have decoration.
- The porcelain is now packed and ready to be transported.

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College of Engineering and Technology
Department of Chemical Engineering

MANUFACTURING COMPANIES IN THE PHILIPPINES


1. Philinco International Corporation
- Cavite, Philippines
- Decorated Dolomite and Porcelain Plates
2. CSM Philippines Inc.
- Binan, Laguna
- Assorted Porcelain Decorations
3. Currey International Inc.
- Pampanga Housewares

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

PLANT LAYOUT

PROCESS LAYOUT

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

STRUCTURAL CLAY PRODUCTS

Structural clay products are


lowcost but are very durable products.
Examples of these are building bricks,
face bricks, terra-cotta, sewer pipe and
drain tile. These are commonly
manufactured without the need of
glazing.

WHAT IS A BRICK?

The term brick refers to small


units of building material, often made
from fired clay and secured with
mortar, a bonding agent comprising of
cement, sand, and water.

They are usually four inches


wide and twice as long, brick is an
ideal material for structures in
confined spaces, as well as for curved
designs. Moreover, with minimal upkeep, brick buildings generally last a long
time.

RAW MATERIALS FOR BUILDING BRICKS

The raw materials for building bricks is almost the same with a whiteware.
Building bricks comprises of clay, feldspar and flint as well. However, the clay
used for the manufacturing process is different with that of a whiteware. There
are three kinds of clay used for the manufacturing of building bricks.

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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Red Burning Clay

White Burning Clay

Buff Burning Clay

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College of Engineering and Technology
Department of Chemical Engineering

MANUFACTURING PROCESS OF BUILDING BRICKS


PROCESS EQUIPMENT USED
Grinding, Crushing and Screening
- The raw materials are grinded for
easier processing.
- A screener filters out the oversize to
return to the grinding machine.
Equipment Used: Jaw Crusher
Extrusion
- Pulverized material and water are fed
into one end of a pug mill.
- The extruder usually consists of two
chambers. The first removes air from
the ground clay with a vacuum, thereby
preventing cracking and other defects.
- The second chamber, a high-pressure
cylinder, compacts the material into the
shape of a brick.
Equipment Used: Vacuum Pug
Mill/Extruder
Drying
- Before the brick is fired, it must be
dried to remove excess moisture. If this
moisture is not removed, the water will
burn off too quickly during firing,
causing cracking.
Equipment Used: Tunnel Dryer

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College of Engineering and Technology
Department of Chemical Engineering

Firing
- The kiln is basically a giant oven. It fires
the bricks at 1040°C or 2000°F.
- This is where the bricks got its reddish
color
Equipment Used: Tunnel Kiln
Setting and Packaging
- After the brick is fired and cooled, it is unloaded from the kiln
- The packaged brick is then shipped to the job site, where it is typically
unloaded using boom trucks.

MANUFACTURING COMPANIES IN THE PHILIPPINES

TOPBLOCK CORPORATION MILESTONE ENTERPRISES


Norzagaray, Bulacan Balintawak, Quezon City

EZ ROCKS CO. & INC. RIVIERA FILIPINA INC.


Makati City Quezon City

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College of Engineering and Technology
Department of Chemical Engineering

PROCESS LAYOUT

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College of Engineering and Technology
Department of Chemical Engineering

REFRACTORIES

What is a refractory?

The word refractory comes from the


French réfractaire, meaning “high-melting.” Refractory
is any material that has an unusually high melting point
and that maintains its structural properties at very
high temperatures. A refractory material is a type of
engineering ceramic called an ‘industrial ceramic’.
Composed principally of ceramics, refractories are
employed in great quantities in
the metallurgical, glassmaking, and ceramics
industries, where they are formed into a variety of shapes to line the interiors
of furnaces, kilns, and other devices that process materials at high
temperatures.

Classifications of Refractories:

A. Based on Chemical Composition

1. Acidic refractories - consist of mostly acidic materials


like alumina (Al2O3) and silica (SiO2). They are generally not attacked or
affected by acidic materials, but easily affected by basic materials. They
include substances such as silica, alumina, and fire clay brick refractories.
Notable reagents that can attack both alumina and silica are hydrofluoric
acid, phosphoric acid, and fluorinated gases (e.g. HF, F2). At high
temperatures, acidic refractories may also react with limes and basic
oxides.

2. Neutral refractories - These are used in areas where slags and


atmosphere are either acidic or basic and are chemically stable to both
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Department of Chemical Engineering

acids and bases. The main raw materials belong to, but are not confined
to, the R2O3 group. Common examples of these materials
are alumina (Al2O3), chromia (Cr2O3) and carbon.

3. Basic refractories - These are used in areas where slags and atmosphere
are basic; they are stable to alkaline materials but could react with acids.
The main raw materials belong to the RO group to which magnesia (MgO)
is a very common example. Other examples include dolomite and chrome-
magnesia. For the first half of the twentieth century, the steel making
process used artificial periclase (roasted magnesite) as a lining material for
the furnace.

B. Based on Method of Manufacture


1. Dry press process - This process is ideally suitable to the formation of simple
solid shapes. It is particularly suited to clays of very low plasticity. Clay is
mixed with a minimal amount of water, then pressed into steel molds under
pressures by hydraulic or compressed air rams. Because the dry press
process is so simple and involves low capital equipment costs it is the most
widely used high –volume forming process for ceramics.
2. Fused cast - Fused cast involves melting refractory material in a electric
furnace followed by casting and annealing are treated with oxygen while in
the molten state to place the constituents in the most highly oxidized state.
This method minimizes the exudation of the glassy matrix of the refractory
during service. The raw materials for the refractories may be oxidized before
melting by heat treating to reduce the oxygen necessary for oxidizing the
molten refractory. High density, small or large shapes are obtained. When
appropriate, a finish is made by grinding with diamond tools.
3. Hand molded - The mold is made by hand. Hand molded refractories do not
have the smooth surface of machine made brick. This method is especially
well adapted to small.

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Department of Chemical Engineering

4. Formed - Firebrick is a common example of formed refractory. Formed


refractories are manufactured by either fired or chemically bonded method.
Fired refractories is formed by heating the refractory material to high
temperatures in a kiln to form a ceramic bond. This process gives the raw
materials their refractory properties.
Chemically bonded refractory brick, also referred to as unfired brick, is formed
with the aid of selected additives that set up at room temperature and provide
structural integrity, eliminating the need for high-temperature sintering. It
offers significant energy savings by eliminating the need for high-temperature
processing. In addition, the many methods for modifying the chemical bond
can develop new compositions to withstand a variety of severe environments
encountered in many industrial processes.
5. Un-formed - Un-formed refractories, also called monolithic, do not comes in
any specific form. Unformed refractories are made and marketed in
granulated or plastic forms or as spray mixes. Thus, they can be used as
patching materials for maintenance. Common unformed refactories include
monolithic-plastic, ramming and gunning mass, castables, mortars, and dry
vibrating cements. They are manufactured in various ways.

C. Based on Fusion Temperatures


1. Low heat duty refractories
- For low temperature environment (1520 – 1630 °C)
2. Medium heat duty refractories
- For temperature ranging from 1630 – 1670°C
3. High heat duty refractories
- For temperature ranging from 1670 – 1730°C
4. Super duty refractories
- For temperature above 1730°C

32 | P a g e
Ceramic Industry
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Department of Chemical Engineering

Varieties of Refractories

About 95 percent of the refractories manufactured are non-basic, with


silica (acid) and fire-clay (neutral) brick predominant. Although a refractory
usually thought of in terms of its ability to withstand temperature, it is really
only in exceptional cases that heat is the sole agent that affects the final
destruction. It is usually caused by chemical action at the operating
temperature.

1. Fireclay refractories - Fireclay refractories are


essentially hydrated aluminum silicates with 25%
- 45% Al2O3 and 50% - 80% SiO2 and minor other
minerals. As fireclay brick is relatively cheap and
its raw materials are widespread, it is the most
common type of refractory brick and used widely
in most furnaces, kilns, stoves, regenerators, etc.
2. Silica brick - Silica brick is a refractory material containing at least 93% SiO2.
The raw material is quality rocks. Silica brick has
excellent mechanical strength at temperatures
approaching their actual fusion point. This
behavior contrasts with that of many other
refractories, for example alumino-silicate
materials, which begin to fuse and creep at
temperatures considerably lower than their fusion
points. Various grades of silica brick have found
extensive use in glass making and steel industry.

33 | P a g e
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College of Engineering and Technology
Department of Chemical Engineering

3. High alumina refractories - Alumina refractories containing more than 45%


alumina are generally termed as high alumina
materials. The alumina concentration ranges from
45 to 95%. Commonly used refractory are
sillimanite (61%), mullite (70 –85%) and
corundum (99%). The refractoriness of high
alumina refractories increases with increase in
alumina percentage. The applications of high
alumina refractories includes the hearth and shaft of blast furnaces, lime and
ceramic kilns, cement kilns, glass tanks and crucibles for melting a wide range
of metals.
4. Magnesite refractories - Magnesite refractories are chemically basic materials,
containing at least 85% magnesium oxide. These
are made from naturally occurring magnesite
(MgCO3) and Silica (SiO2). The physical properties
of this class of brick are generally poor, and their
great value is primarily in their resistance to basic
slags, particularly to lime and iron rich slags.
These constitute the most important group of refractories for the basic
steelmaking processes. In addition to metallurgical furnaces, basic brick are now
being successfully used in glass tank checkers and in lime and cement kilns.
5. Chromite refractories - Chrome-magnesite material usually contain 15-35%
Cr2O3 and 42-50% MgO whereas magnesite-
chromite refractories contain at least 60% MgO
and 8-18% Cr2O3. Chrome- magnesite
refractories are used for building the critical
paths of high temperature furnaces. These
materials can withstand corrosive slags and
gases and have high refractoriness. The
magnesite-chromite products are suitable for

34 | P a g e
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College of Engineering and Technology
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service at the highest temperatures and in contact with the most basic slags used
in steel melting. Magnesite-chromite usually has a better spalling resistance than
chrome-magnesite.
6. Zirconia refractories - Zirconia refractories have a very high strength at room
temperature which is maintained up to
temperatures as high as 15000C. Its thermal
conductivity is found to be much lower than that
of most other refractories. Zirconia also does not
react readily with liquid metals and molten
glasses. They are, therefore, useful as high
temperature constructional materials for
metallurgical furnaces and glass furnaces.
7. Monolithic refractory - Monolithic refractory, the
name generally given to all unshaped refractory
products, are materials installed as some form of
suspension that ultimately harden to form a solid
mass. Monolithic refractories are replacing the
conventional type fired refractories at a much faster
rate in many applications including those of
industrial furnaces.
8. Insulating materials - Insulating materials are high
porosity refractories with low thermal conductivity
used in order to reduce the heat losses. Insulating
materials has a lower density and offers higher
thermal resistance compared to firebricks. In all
cases, thermal conductivity of the insulation
increases significantly as temperature increases. A
wide range of insulating refractories with wide combinations of properties are
now available. It is likewise cheaper in contrast to the high duty bricks.

35 | P a g e
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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Uses and Applications

The greatest user of


refractory materials is the iron and
steel industry (70% of total use),
while other significant consumers
are the cement and lime, ceramic,
glass, chemical, nonferrous and
foundry industries.

Refractories are meant to


sustain at high temperature so the very common applications are:

 Used in furnaces such as blast furnace and kilns such as coke oven.
 Used in boilers.

Properties

In making the refractory best suited for a definite operation it is necessary


to consider the materials, the working temperature of the furnace where the
refractory is needed, the rate of temperature change, the load applied during
heats, and the chemical reactions encountered. Generally, several types of
refractories are required for the construction of any one furnace, because usually
no single refractory can withstand all the different conditions that prevail in the
various parts of furnaces.
A. Physical

Porosity. Porosity is directly related to many other physical properties of


brick, including resistance to chemical attack. The higher the porosity of
the brick, the more easily it is penetrated by molten fluxes and gases. For
a given class of brick, those with the lowest porosity have the greatest
strength, thermal conductivity, and heat capacity.
36 | P a g e
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College of Engineering and Technology
Department of Chemical Engineering

Fusion Points. Fusion points are found by the use of pyrometric cones of
predetermined softening points. Most commercial refractories soften
gradually over a wide range and do not have sharp melting points because
they are composed of several different minerals, both amorphous and
crystalline. The fusing points of these pyrometric cones are available in the
literature.

Spalling. A fracturing, or a flaking off, of a refractory bricik, or block, due


to uneven heat stresses or compression caused by heat is known as
spalling. Refractories usually expand when heated. Bricks that undergo
the greatest expansion at the least uniform rate are the most susceptible
to spalling when subjected to rapid heating and cooling.

Strength. Cold strength usually has only a slight bearing on strength at


high temperatures. Resistance to abrasion or erosion is also important for
many furnace constructions, such as by-product coke-oven walls and
linings of the discharge end of rotary cement kilns.

Resistance to Temperature Changes. Bricks with the lowest thermal


expansion and coarsest texture are the most resistant to rapid thermal
changes; also, less strain develops, Bricks that have been used for a long
time are often melted to glassy slags on the outside surface or even more
or less corroded away.

Thermal Conductivity. The densest and least porous bricks have the
lightest thermal conductivity. Though heat conductivity is wanted in some
furnace constructions, as in muffle walls, it is not so desirable as some
other properties of refractories, such as resistance to firing conditions.
Insulation is desired in special refractories.

37 | P a g e
Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Heat Capacity. Furnace heat capacity depends upon the thermal


conductivity, the specific heat, and the specific gravity of the refractory

B. Chemical

The usual classification of commercial refractories divides them into


acid, basic, and neutral groups, although in many cases a sharp
distinction cannot be made. Silica bricks are decidedly acid, and
magnesite bricks are strongly basic; however, fire-clay bricks are generally
placed in the neutral group, though they may belong to either of these
classes, depending upon the relative silica-alumina content. It is usually
inadvisable to employ an acid brick in contact with an alkaline product, or
vice versa. Neither chemical reactions nor physical properties are the only
criteria of acceptable behavior; both should be considered. Chemical
action may be due to contact with slags, fuel ashes, and furnace gases, as
well as with products such as glass or steel.

38 | P a g e
Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Manufacturing Companies in the Philippines

1. Specialized Products & Services Inc.


3rd Flr., Orcel II Bldg.
1611 Quezon Ave., Quezon City

2. Assistco Energy and Industrial Corporation


First Avenue corner Antonio Drive,
Bagumbayan, Taguig City 1632

3. ABC Commodities Corporation


# 16 Rosal Street Bahayang Pag-asa,
Maysan Road, Valenzuela City 1442

4. Refracore Corporation
Unit 205 Philam Life Bldg. J. Luna cor Lluch Sts.
Iligan City

39 | P a g e
Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Manufacturing Process of Fire Bricks

The most common refractory is the fire brick that can be found usually
at fireplaces at home or in other industry that requires too much heat in the
production. Dense firebricks are the ones that are used with extreme
mechanical, chemical or thermal stresses.

A. Plant Layout

40 | P a g e
Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

B. Equipment Layout

41 | P a g e
Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

C. Unit Operations and Processes

Unit Operation and Description Equipment


Process
Collection of Raw The excavation site is Excavator
Materials dug to obtain the shale
needed for the
production. It will be
exposed to elements
for two years before
processing. This will
make the processing
easier.

Clay Proportioning The delivered shale Crusher and Screener


and clay from the
excavation site is
crushed and screened
separately or in
combination
depending on the
type of brick needed.

42 | P a g e
Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Pugging The combination of Pug Mill


shale and clay will be
mixed with water to
form a slurry.

Rolling This process is done Grinding Wheel


to further grind the
shale and clay mixture
into powder using a 4ft
high stone wheel with
a steel tire that grinds
50 tons of shale per
hour.
Mixing After the mixture Extrusion Machine
is fully pulverized,
the addition of
coloration and
conditioning additives
takes place.
Coloration is usually
made up of oxide
minerals like zinc and
iron. Conditioning

43 | P a g e
Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

additives are usually


lime and magnesium
oxide.
Moulding The mixture will be Extrusion Machine
forced out to an
extrusion machine to
form a one long
continuous piece
called a slug. Then, it
is textured to create a
common design and a
giant knife will cut the
slug into 5ft length.
There are holes on the
brick to control the
weight of the brick
depending on its Molder
application. The 5ft
slug will be cut into
several small pieces
then separates and
stacks them
accordingly.

44 | P a g e
Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Drying During the stacking Dryer


process, the bricks
slowly evaporate its
water content. It will
be kept for 2 days for
slow-drying. Slow-
Drying is necessary to
prevent the bricks
from breaking.
Kilning The kiln is basically a Kiln
giant oven. It fires the
bricks at 1040°C or
2000°F. This is where
the bricks got its
reddish color.

Quality Testing Before storing, the Measuring Tools


bricks will be tested if
it meets the certain
specification of the
demanded type of
brick. Its weight,
volume and water
absorbency is
important for the
testing. The brick will
be cut in half and

45 | P a g e
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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

submerged in water for


24hrs. Comparing its
weight before and after
soaking, the quality
tester can determine
its water absorbency.

Storing and When the batch Stacking Machine


Packaging passed the quality
testing, it will be
stacked to prepare for
packaging and storing.

46 | P a g e
Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

SPECIALIZED CERAMIC PRODUCTS

CERAMIC COMPOSITES

Structures of metallic honeycombs or webbings, impregnated with a


ceramic phase, derive strength from high-alloy metals and good thermal
properties from ceramic foams. The temperature limits of such bonded materials
are exceedingly high; they are employed for aerospace hardware such as heat
shields, rocket nozzles, and ram-jet chambers.

Cermets comprise one of a group of composite materials consisting of an


intimate mixture of ceramic and metallic components, usually in the form of
powder. These are compacted and sintered to obtain certain physical properties
not found solely in either of the components.

Cermets

Reaction bonded ceramic-metal composites are formed by a chemical


reaction that bonds the two materials when heated below the melting point of
either. The ceramic acts as a catalyst to cause corrosion of the metal to a metal
oxide. The bond is extremely strong and permanent and forms quickly, although

47 | P a g e
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College of Engineering and Technology
Department of Chemical Engineering

for optimum strength the two materials are usually kept hot for several hours
while clamped together. This bonding can occur between all metals and most
ceramics, but the strongest bonds are formed between the:

 Noble metals (such as platinum, gold, and silver)

 Oxide ceramics of alumina, magnesia, silica, zirconia, and beryllia

Alumina Silica Beryllia

Magnesia Zirconia

48 | P a g e
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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Several applications for these materials are suggested such as:

 gold-coated ceramic wafers for  ceramic-capped gold dental


semiconductor chips crowns

 zirconia-lined steel for


corrosion resistant uses

FERROELECTRIC AND FERROMAGNETIC CERAMICS

The most common ceramic type in this class is barium titanate (BaTiO3).
Titania and its compounds exhibit unusual properties useful in electrical
applications, the most important of which involves high capacity at various
frequencies.

Procedures used in fabricating titania and titanate bodies are ceramic in


character. Ferromagnetic ceramic materials have been responsible for important
advances in the design of electronic equipment.

49 | P a g e
Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

HIGH-ALUMINA CERAMICS

These are mechanically strong, dense materials, unlike refractories which


are usually porous.

Most high-alumina ceramics are used to take advantage of their wear


resistance, corrosion resistance, and dimensional stability rather than their
ability to resist high temperatures.

High-alumina ceramics are used for:

Mining chutes and Respirator valves Precision machine


slides components

Insulators for electrostatics precipitators

50 | P a g e
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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

VITREOUS ENAMEL

Porcelain or vitreous enamel is a ceramic mixture containing a large


proportion of fluxes, applied cold and fused to the metal at moderate red heat.
The application of enamel to gold, silver, and copper is one that dates to the
ancients.

Long valued as a material to great beauty in the field of decorative art, it


has come into general commercial use because it provides a product of great
durability and wide application.

Current uses are in plumbing fixtures, cooking utensils, industrial


equipment, and glass-enameled steel for chemical use.

The household appliances market has been diminished by the modern


use of baked-on organic coating, but new markets have developed in
electroluminescent lighting and in the automobile industry.

Raw Materials

The raw materials used in the enamel industry may be divided into six
different groups: refractories, fluxes, opacifiers, colors, floating agents, and
electrolytes.

 Refractories- contribute to the acidic part of the melt and give body to the
glass. These include materials such as quartz, feldspar, and clay.
 Fluxes- basic in character and react with the acidic refractories to form
the glass. These include such products as borax, soda ash, cryolite, and
fluorspar.
 Opacifiers- compound added to the glass to give it the white opaque
appearance so characteristic of vitreous enamels. There are two principal
51 | P a g e
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College of Engineering and Technology
Department of Chemical Engineering

types: insoluble opacifiers (titanium dioxide, tin oxide, and zirconium


oxide) and devitrification opacifiers (cryolite and fluorspar).
 Color- may be oxides, elements, salts, or frits, and may act either as
refractories or as fluxes.
 Floating agents- chosen to suspend the enamel in water such as clay and
gums.
 Electrolytes- to peptize the clay and properly suspend the enamel. These
include material such as borax, soda ash, magnesium sulfate, and
magnesium carbonate.

Manufacture of the Frit

The preparation of the enamel glass, or frit, is similar to the first stages of
the manufacture of ordinary glass. The raw materials are mixed in the proper
proportions and charged into a melting furnace maintained near 1370°C, from 1
to 3 h. After the batch has been uniformly melted, it is allowed to pour from the
furnace into a quenching tank of cold water, shattering the melt into millions of
friable pieces. This material is called frit. Enamel is normally made in a wet
process by grinding the ingredients, principally a mixture of frit and clay.

Preparation of Metal Parts

The success of enameling depends on the nature and uniformity of the


metal base to which the enamel is fused and on obtaining a parallelism between
the coefficients of expansion of the enamel and the metal.

The sheet-metal enameler usually purchases sheets to meet a definite


specification. Before the liquid enamel (suspension in water) is applied to the

52 | P a g e
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College of Engineering and Technology
Department of Chemical Engineering

metal, the surface must be thoroughly cleaned of all foreign matter. Sheet metal
is cleaned by pickling inn dilute hydrochloric or sulfuric acid at 60°C after the
iron has been annealed.

The advent of the powder application has brought with it the pickle-free
metal preparation. Efforts are being made to perfect a no-pickle wet process.

Application of the Enamel

 Dipping
 Slushing
 Spraying

In the powder process the steel is coated by electrostatic spraying. This


process is evolving to a two-coat, one-fire system consisting of a thin powder
base coat and a powder cover coat.

Firing

All enamels must be fired on the ware to melt them into a smooth,
continuous, glassy layer. The requirements for successful firing of a good
enamel:

 Proper firing temperature, 750 to 800°C


 Time, 1 to 15 min
 Proper support of the ware
 Uniform heating and cooling of the ware
 An atmosphere free from dust

53 | P a g e
Ceramic Industry
Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

REFERENCES

Austin, George T. (1885) Shreve’s Chemical Process Industries. 5th Edition

How Bricks are Made Retrieved 11 Nov 2016 from

http://www.madehow.com/Volume-1/Brick.html

How Porcelains are Made Retrieved 11 Nov 2016 from

http://www.madehow.com/Volume-1/Porcelain.html

Lily, R. p. (2015, April 30). The Common Manufacturing Methods Of Refractories.


Retrieved from Refractory Brick Over-blog: http://refractorybrick.over-
blog.com/2015/04/the-common-manufacturing-methods-of-
refractories.html

Mason, T. O. (2016, October 2). Refractory. Retrieved from Britannica


Encyclopedia: https://www.britannica.com/technology/refractory

Process of refractory making. (n.d.). Retrieved December 2, 2015,


from http://www.krosaki.co.jp/english/c4/c_4_1_1.html

The Brick Making Process Retrieved 11 Nov 2016 from

http://forest.mtu.edu/pcforestry/resources/studentprojects/bricks/pro
cess.htm

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