CERAMICS

Comprise all engineering materials/products that are

chemically inorganic, except metal/metal alloys, and are
usually rendered serviceable through high temperature
processing.

Ceramics vs. Metals

Primary difference is the nature of chemical bonding. Ceramics have
combination of ionic and covalent bonding w/c result in high elastic
modulus and hardness, high melting points, low thermal expansion,
and good chemical resistance. On the other hand, metals exhibit
metallic bonding.
CERAMICS: Properties
• Durability
• strength and brittleness
• high electrical and thermal resistance
• ability to withstand the damaging effects of acids, oxygen, and
other chemicals because of their inertness
• HISTORY of Ceramic Industry
• USES and ECONOMICS
• BASIC RAW MATERIALS
• Classification of Ceramics
✓ Whitewares
✓ Structural Clay Products
✓ Refractories
✓ Specialized ceramic products
✓ Enamels and enameled metal
• Manufacturers in the Philippines
• 15000 B.C. – Burnt clayware was dated
- records of culture (museums)
Modern methods of fabrication: cross-fertilization of silicate chemistry with
metallurgy and solid-state physics coupled with advanced automation and
computer-controlled processes.
• Recently new processes: brickmaking from inorganic wastes
(fly ash, foundry sand, mine tailings, furnace slag etc.
USES and ECONOMICS

• Refractories use large

quantities of clay
• Clays are used as
fillers in many
products (paper,
rubber, plastics etc)
• Fuller’s earth – used
in adsorbent
application
• Other uses pottery,
floor and wall tile etc.
Basic Raw Materials

Clay Feldspar Sand

8
1. Clay
Kaolinite (Al2O3∙2SiO2∙2H2O)
- basic clay mineral used in ceramic industry.
Bentonite Clay –based on montmorillonite [(Mg, Ca)O∙Al2O3∙5SiO2∙nH2O]
- for very high plasticity
Beneficiation procedure – to remove sand and mica
2. Feldspar
– Important fluxing constituent in ceramic formulas
3 common types:
a. Potash (K2O∙Al2O3 ∙6SiO2)
b. Soda (Na2O ∙Al2O3 ∙6SiO2)
c. Lime (CaO ∙Al2O3 ∙6SiO2)
3. Sand
- Also called flint
- Used for light-colored ceramic products.

Fluxes
- A wide variety of other minerals, salts, and oxides used as special refractory
ingredients, to lower vitrification temperature, melting temperature or reaction
temp. Ex: common special refractory ingredients
- Examples: Alumina

Borax Chromite

Soda Ash Magnesite

Pearl Ash Zirconia

Fluorspar Titania
Carborundum
Cryolite
Mullite
Table 1. Basic Raw Materials for Ceramics

KAOLINITE FELDSPAR SAND/FLINT

FORMULA Al2O3∙2SiO2∙2H2O K2O∙Al2O3 ∙6SiO2 SiO2

PLASTICITY Plastic Nonplastic Nonplastic

FUSIBILITY Refractory* Easily fusible binder Refractory*

MELTING POINT 1785°C 1150°C 1710°C

SHRINKAGE Much shrinkage Fuses No Shrinkage

*Infusable at highest temperature of coal fire (1400 °C)
 Chemical Conversions

1. Dehydration (“Chemical water smoking”) at 150 to 650 °C

2. Calcination e.g. of CaCO3 at 600 to 900 °C
3. Oxidation of ferrous iron and organic matter at 300-900 °C
4. Silicate formation at 900 °C and higher
 Classifications of Ceramic Products based on degree of
vitrification

1. Whitewares – varying amounts of fluxes & vitrification, heat at moderately high T.

2. Heavy-clay products – abundant fluxes, heat at low T, little vitrification
3. Refractories – few fluxes, heat at high T, little vitrification
4. Enamels - very abundant fluxes, heat at moderate T, complete vitrification
5. Glass – moderate fluxes, heat at high T, complete vitrification
-generic term for fine
and white texture.
Classifications of Whiteware based on degree of vitrification
- semivitreous dinnerware; porous & non-
Earthenware translucent w/soft glaze

– vitrified translucent ware w/ medium glaze w/c

Chinaware resists abrasion to max. degree. Used for non-
technical purpose.

– vitrified translucent ware w/ hard glaze. Includes

Porcelain chemical, insulating and dental porcelain.

Sanitary ware – formerly made from clay, usually porous

- One of the oldest ceramic wares; regarded as

Stoneware “crude porcelain”

Whiteware tiles - Classified as floor tiles; resistant to abrasion.

Classifications of Whiteware based on degree of vitrification

Earthenware Porcelain Stoneware

Chinaware Sanitary ware Whiteware tiles

Manufacture of Porcelain
3 lines of production of porcelain:
1. Wet-process 2. Dry-process
porcelain porcelain 3. Cast porcelain

-fine-grained, - for rapid - for making of

highly glazed production of more pieces too large/
insulators for high open-texture, low too intricate
voltage device voltage pieces.

*same raw materials, differs in drying and forming(shaping) steps.

Manufacture of Porcelain: Wet Process
Manufacture of Porcelain: Wet Process
Jiggering - plastic clay is pressed into or on a single revolving mold, the potter often being
aided in shaping the outer surface & removing excess clay by a lever, which is lowered over
the mold shaped in the profile of the object desired.
Manufacture of Porcelain: Wet Process

Glazing – coating of thin glass melted onto the surface of more-or-less

ceramic products.
Glaze – contains 2 distinct types in different proportions of refractory
materials (feldspar, silica etc. ) and fluxes.
Glost firing – technical term for the firing of glaze.

Nepheline syenite – permits firing at lower temp.

 - used to withstand the
thermal, chemical, and
physical effects met with in the
furnace procedures
Properties of Refractories
I. Chemical Properties
Usual Classification of commercial refractories:

Acidic Ex: Silica bricks

Basic Ex: Magnesite bricks
Neutral Ex: Fireclay bricks (depends on
relative silica-alumina content
Properties of Refractories
II. Porosity
- ↑ porosity = more easily penetrated by molten fluxes and
gases
- A given class brick, lowest porosity have the greatest
strength, thermal conductivity and heat capacity.
III. Fusion Points

- Found by the use of pyrometric

cones of predetermined softening
points
Properties of Refractories
IV. Spalling
-Fracturing or flaking off of refractory brick due to uneven heat
stresses or compression caused by heat.
-Bricks that undergo greatest expansion at the least rate are the
most susceptible when subjected to rapid heating/cooling.

V. Strength

Resistance to abrasion – important for furnace construction.

Properties of Refractories
VI. Resistance to temperature changes

-Bricks w/ lowest thermal expansion and coarsest texture

are the most resistant to thermal changes.

VII. Thermal conductivity

-Densest and least porous bricks have the highest thermal

conductivity.
Properties of Refractories

VIII. Heat Capacity

-depends on thermal conductivity , specific heat, and

specific gravity.
- The low quantity of heat absorbed by lightweight brick
works as an advantage for furnaces operated intermittently,
because the working temperature can be obtained in less
time with less fuel.
Manufacture of Refractories
The following are physical operations and chemical conversions used:
Grinding and Screening
Size of the particles – one of the most important factors
- proportion of coarse and fine particles is 55:45
which gives the densest mixture
Screening – necessary for close control along with separation and
recycling.
Mixing
- For distribution of the plastic material to coat the non-plastic material
- For providing a lubricant during the molding operation & permits
bonding of the mass w/ min. no. of voids
Manufacture of Refractories

Drying
- To remove moisture added to develop plasticity.
- Causes high shrinkage and internal strains

Molding
Dry-press method –w/ mechanically operated presses.
- suited for nonplastic materials
For high-pressure forming, it requires to de-air the bricks to avoid
laminations and cracking.
Manufacture of Refractories

Burning

- Maybe carried out in typical round, downdraft kilns or continuous

tunnel kilns.
- 2 important things taking place: (1) Development of permanent
bond by partial vitrification of the mix and (2) development of
stable minerals forms for future service
- Removal of water of hydration, calcination of carbonates and
oxidation of ferrous iron.
- Volume shrinks (30%) but can be eliminated by pre-stabilization of
materials
Varieties of Refractories
-most widely used.
For linings of blast furnace,
Fire Clay
stoves, open hearths and other
furnace.

-95-96% SiO2 & 2 % lime added

for grinding to furnish bond.
Silica Brick For by-product coke and gas
retorts due to high thermal
conductivity.

-can withstand sever

conditions where silica and
High-Alumina Refractories fireclay are not suitable. For
lining of glass furnaces, high-
pressure oil stills etc.
Varieties of Refractories

-made from magnesia,

Basic Refractories
chromite and forsterite.

- Made from domestic

magnesites/ magnesia
Magnesia Refractories extracted from brines. Do not
stand much load at higher
temp.

2 types: for backing refractory

bricks (porous DE);
Insulating Bricks replacement for regular
refractory (“lightweight
refractories”).
Varieties of Refractories
-extremely refractory, has high
thermal conductivity, low
Silicon Carbide
expansion and high resistance
to abrasion and spalling.

-Mullite and corundum have

Refractories from Crystalline high slag resistance and remain
Alumina/ Aluminum Silicates in crystalline state at temp.
>1600°C

-employed in glass furnaces,

linings of hot zones of rotary
Electrocast or Corhart
kilns, modern boiler furnaces
Refractories
exposed to severe duty, forging
furnace (metallurgy).
Varieties of Refractories
-superior qualities are based
mostly on freedom from
fluxes.
-refractory oxides : alumina,
magnesia, zirconia, beryllia, &
thoria.
Pure Oxide Refractories
• Sinter alumina - has widest
application (temp <1870°C)
• Magnesia –basic refractory
(<2200°C)
• Zirconia- temp range (2550-
2600°C
Specialized Ceramic products

Ceramic Composites
-Temperature limits of bonded materials is extremely high.

Cermets- comprise one of a group of composite mat. consisting of

mixture of ceramic &metallic components compacted & sintered to
obtain certain physical properties not found solely in either components.

Ferroelectric and Ferromagnetic ceramics

Most common type is barium titanate (BaTiO3)- for

electrical applications due to high capacity at various
frequency.
Specialized Ceramic products

High Alumina Ceramics

-mechanically strong, dense materials, unlike refractories w/c are usually
porous.
-wear resistant, corrosion resistant, dimensionally stable rather than the
ability to resist high temp.
-85% or more by wt. Al2O3
 -ceramic mixture
containing large
proportions of fluxes.
Vitreous Enamel

Raw Materials
1. Refractories – quartz, feldspar, and clay w/c contribute to acidic part of
the melt and give body to the glass
2. Fluxes – borax, soda ash, cryolite, and fluorspar (basic & react w/
acidic refractories to form glass)
3. Opacifiers – compounds added to the glass to give white opaque
appearance
• Insoluble opacifiers (TiO2, Tin oxide and zirconium oxide)
• Devitrification opacifiers (cryolite and fluorspar)
Vitreous Enamel

Raw Materials
4. Color – oxides, elements, salts, or frits (act as refractories/fluxes.
5. Floating agents – clays and gums chosen to suspend the enamel in water.
6. Electrolytes – borax, soda ash, MgSO4, MgCO3 –
Kilns

Continuous Kilns
-the most important kilns, continuous car tunnel
kilns used for firing brick, tile, porcelain,
tableware and refractories.
2 types:
(1) Direct-fired type – combustion gases burn
directly among the wares
(2) Indirect (muffle) type – products of
combustion are not allowed to contact the
wares.
Kilns
Periodic Kilns
- Not fuel efficient but are more versatile.
Downdraft kilns – round or rectangular in shape,
for burning face brick, sewer pipe, stoneware,
tile and common brick.
- heat is raised form room temp. to
finishing temp. for each burning
operation.
- “Downdraft” – because products of
combustion go down in passing over the
wares set in the kiln.
- “updraft”- commonly used for burning
pottery.
Common bricks are burned in scove kilns, built
for green brick, and the outside walls is daubed
or “scove” with clay.
Manufacturers in the Philippines

Valenzuela, Metro
Manila

Sta. Rosa,
Laguna