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What is a Ceramic?
The word is traced back to the Greek term keramos, meaning potters clay or pottery.
Keramos in turn is related to an older Sanskrit root meaning to burn. Ceramus or Keramos
was also an ancient city on the north coast of the Aegean Sea in what is currently Turkey.
In the most simple of terms, ceramics are inorganic, nonmetallic materials. They are typically
crystalline in nature (have an ordered structure) and are compounds formed between metallic
and nonmetallic elements such as aluminum and oxygen (alumina, Al2O3), calcium and
oxygen (calcia, CaO), and silicon and nitrogen (silicon nitride, Si3N4).
In broader terms ceramics also include glass (which has a non-crystalline or amorphous
random structure), enamel (a type of glassy coating), glass-ceramics (a glass containing
ceramic crystals), and inorganic cement-type materials (cement, plaster and lime). However,
as ceramic technology has developed over time, the definition has expanded to include a
much wider range of other compositions used in a variety of applications.
Ceramic Classifications (or types)
There are two major categories of glasses and ceramics: traditional and advanced.
Traditional applications include consumer products like dinnerware or ovenware and
construction products like tile or windows. Most of these applications have been in use for
many years.
Advanced applications take advantage of specific mechanical/electrical/
optical/biomedical/chemical properties of glass or ceramic materials and have entered the
scene over the last several decades or so.
The two major categories can be further broken down into more specific product
classifications or market segments as seen in the tables below. One category that is
sometimes hard to define is refractories. The production of most ceramics and glasses, as well
as other commodities like metals, metal alloys, and cement, would not be possible without
these materials. Refractories are critical materials that resist aggressive conditions, including
high temperature (up to 2000C), chemical and acid attack, abrasion, mechanical impact, and
more.
Hence, refractory ceramics are little known, enabling materials that play a crucial role in
allowing all commodity manufacturers to operate efficiently and profitably, thus supporting
the global economy. Although refractories are typically categorized as a traditional
application since the market is mature, their high performance makes them more of an
advanced material. In fact, one global market estimate for advanced ceramics includes kiln
furniture, which is estimated at around $211 million.
Traditional Segments
Segment
Products
Structural clay Brick, sewer pipe, roofing tile, clay floor and wall tile (i.e., quarry tile),
products
flue linings
Whitewares
Refractories
Glasses
Flat glass (windows), container glass (bottles), pressed and blown glass
(dinnerware), glass fibers (home insulation)
Abrasives
Cements
Advanced Segments
Segment
Products
Automotive
Aerospace
Chemical/petrochemical
Coatings
Electrical/electronic
Environmental
Achievement
1. Electrification
2. Automobile
Filters/membranes
Substrates and IC packages,
5. Electronics
capacitors, piezoelectrics, insulators, magnets, superconductors
Glass tubes (CRTs), glass
6. Radio and
television
11. Interstate
highways
13. Internet
20. Highperformance
materials
Ionic Bonding
Ionic bonding occurs between two elements with a large difference in their
electronegativities (metallic and non-metallic), which become ions (negative and positive) as
a result of transfer of the valence electron from the element with low electronegativity to the
element with high electronegativity.
The typical example of a material with Ionic Bonding is sodium chloride (NaCl).
Electropositive sodium atom donates its valence electron to the electronegative chlorine
atom, completing its outer electron level (eight electrons):
As a result of the electron transfer the sodium atom becomes a positively charged ion (cation)
and the chlorine atom becomes a negatively charged ion (anion). The two ions attract to each
other by Coulomb force, forming a compound (sodium chloride) with ionic bonding.
Ionic bonding is non-directional.
Covalent Bonding
Covalent bonding occurs between two elements with low difference in their
electronegativities (usually non-metallics), outer electrons of which are shared between the
four neighboring atoms.
Covalent Bonding is strongly directional.
Ionic-Covalent (mixed) Bonding
Ionic-covalent (mixed) bonding with various ratios of the two fractions (ionic and covalent)
occurs in most of ceramic materials.
Ceramics (ceramic materials) are therefore non-metallic inorganic compounds formed from
metallic (e.g. Al, Mg, Na, Ti, W) or semi-metallic (Si, B) and non-metallic (O, N, C)
elements.
Atoms of the elements are held together in a ceramic structure by one of the following
bonding mechanism: Ionic Bonding, Covalent Bonding, Mixed Bonding (Ionic-Covalent).
Most of ceramic materials have a mixed bonding structure with various ratios between Ionic
and Covalent components. This ratio is dependent on the difference in the electronegativities
of the elements and determines which of the bonding mechanisms is dominating ionic or
covalent.
Electronegativity
In contrast to metallic bonding neither ionic nor covalent bonding form free electrons,
therefore ceramic materials have very low electric conductivity and thermal conductivity.
Since both ionic and covalent bonds are stronger than metallic bond, ceramic materials are
stronger and harder than metals.
Strength of ionic and covalent bonds also determines high melting point, modulus of
elasticity (rigidity), temperature and chemical stability of ceramic materials.
Motion of dislocations through a ceramic structure is impeded therefore ceramics are
generally brittle that limits their use as structural materials.
Ceramics may have either crystalline or amorphous structure. There are also ceramic
materials, consisting of two constituents: crystalline and amorphous.
In general, metals have weaker bonds than ceramics, which allows the electrons to move
freely between atoms. Think of a box containing marbles surrounded by water. The marbles
can be pushed anywhere within the box and the water will follow them, always surrounding
the marbles. This type of bond results in the property called ductility, where the metal can be
easily bent without breaking, allowing it to be drawn into wire. The free movement of
electrons also explains why metals tend to be conductors of electricity and heat.
Plastics or polymers of the organic type consist of long chains of molecules which are either
tangled or ordered at room temperature. Because the forces (known as van der Waals)
between the molecules are very weak, polymers are very elastic (like a rubber band), can be
easily melted, and have low strength. Like ceramics, polymers have good chemical
resistance, electrical and thermal insulation properties. They are also brittle at low
temperatures. The following table provides a general comparison of the properties between
the three types of materials.
Microstructure, which is too small to be seen with the naked eye, plays an important factor in
the final property of a material. For ceramics, the microstructure is made up of small crystals
called grains. In general, the smaller the grain size, the stronger and denser is the ceramic
material. In the case of a glass material, the microstructure is non-crystalline. When these two
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materials are combined (glass-ceramics), the glassy phase usually surrounds small crystals,
bonding them together.
The wide variety of applications for ceramic materials results from their unique properties. In
many respects, these properties cannot be achieved by other materials. Among the many
properties that ceramic products take advantage of include:
high hardness
high mechanical strength
dimensional stability
resistance to wear
resistance to corrosion or chemical attack
weathering resistance
high working temperature
low or high thermal conductivity
good electrical insulation
dielectric and ferroelectric properties
Depending on the composition and the processing of the raw materials, as well as the
fabrication and firing conditions, the properties of the material can often be closely tailored to
the desired application.
General Comparison between Ceramics, Metals and Polymers:
Property
Metal Polymer
Very
Hardness
Very High Low
Low
Elastic modulus Very High High Low
High
temperature
strength
Thermal
expansion
Ductility
Corrosion
resistance
Wear resistance
Electrical
conductivity
Density
Thermal
conductivity
Magnetic
Ceramic
Low
Very
Low
High High
High
Low Low
High
Low
High
Low Low
Depends on
High Low
material
Very
Low
High
Low
Depends on
High Low
material
Depends on
Very
High
material
Low
Note: For general comparison only; specific properties depend on the materials specific
composition and how it is made.
These three material types can also be combined in various ways to form composites to take
advantage of each materials properties. For instance, ceramic particles or fibers can be added
to a ceramic or metal matrix to improve the mechanical properties and/or produce a special
property the matrix by itself generally would not have. Polymers are also reinforced with
glass fibers for a wide range of construction and structural applications.
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The test also found that homes made with brick exceed the 34 mph impact resistance
requirement for high velocity hurricane zones in the Florida building code. Brick also
exceeds Floridas impact resistance requirements for essential facilities in hurricane areas.
Smart Windows Control Light and Heat
Windows have become more intelligent with the help of ceramic particles. Called suspended
particle device technology, a patented technology developed and licensed by Research
Frontiers Incorporated, it allows users to control the amount of light, glare and heat passing
through glass or plastic products such as windows, skylights, doors, sunroofs, visors, eyewear
and more.
Suspended particle devices, more commonly known as SPDs or light valves, use a film
within which droplets of liquid suspension are distributed. Light-absorbing microscopic
particles are dispersed within the liquid suspension. These randomly oriented microscopic
particles are typically made of a black ceramic pigment (chromium iron oxide, copper
chromium oxide, or bismuth manganese oxide). These particles are capable of reflecting heat,
especially near-infrared radiation.
The film is then enclosed between two glass or plastic plates coated with a transparent
conductive material. When no electrical voltage is present, the particles absorb light and
block it from passing through the film. When an electrical voltage is applied, the particles
align so that light can pass through. By regulating the voltage with a simple switch or other
control device, users instantly regulate the amount of light, glare and heat coming through
products such as windows. This gives users a range of transparency where light transmission
can be rapidly varied depending upon the amount of voltage applied.
Clay Roofing Tile Saves Energy
Working with the Oak Ridge National Laboratory, the Tile Roofing Institute reports that tile
roofings mass, reflectivity and ventilation beneath the tiles contribute to a reduction of heat
transference of at least 50%, when compared to a traditional asphalt shingle roof. Coated clay
tiles can cut the transfer of heat by up to 70%. Tile roofing is very fire resistant and also very
durable, withstanding harsh weather conditions like high winds, snow, hail and even
earthquakes. In fact, tile roofs have lasted for centuries, thus making them also very
economical.
and the like. High voltage insulators make it possible to safely carry electricity to houses and
businesses.
Ceramics Improve Antenna Performance
The next generation of mobile phone antennas would not be possible without special
ceramics developed by Morgan Advanced Ceramics for Sarantel, a leading miniature antenna
specialist. Sarantels PowerHelix range uses a patented design in which copper tracks,
deposited onto a small ceramic cylinder, are individually and automatically laser trimmed for
optimum frequency response.
Currently, this type of antenna is used in GPS applications, where its zero ground plane
allows space saving in handheld and portable equipment. When mounted side by side, the
antennas can also be used in combined applications such as Bluetooth and GPS without loss
of performance. However, it is within the mobile phone market that the PowerHelix range
may be of most benefit. Under E-911 Legislation in the United States, it will soon be
mandatory for GPS receivers to be built in to mobile phone handsets, so that the technology
can be used to help emergency services respond more effectively to distress calls. 3G mobile
and Wi-Fi networks are also potential applications.
The continuing debate over the health implications of using mobile phones is another major
issue. International safety regulations defined in terms of the specific energy absorption rate
(SAR) encourage optimization of the ratio of radiated power versus absorbed power in the
user head. The patented PowerHelix antenna design significantly reduces the losses of current
that can cause an incident magnetic field at the users skin. A specific ceramic is used that
enables the manufacture of antennas which yield just five per cent of the radiation emitted by
other systems.
Transistors Advance With Ceramic Material
Intel is combining new high dielectric ceramic and metal materials to build the insulating
walls and switching gates of its 45 nanometer transistors. Transistors are tiny switches that
process the ones and zeroes of the digital world. The gate turns the transistor on and off and
the gate dielectric is an insulator underneath it that separates it from the channel where
current flows.
Hundreds of millions of these microscopic transistors-or switches-will be inside the next
generation of multi-core processors, resulting in record-breaking PC, laptop and server
processor speeds. By replacing the conventional dielectric material with a thicker hafniumbased oxide material, transistor gate leakage is reduced by more than 10 times and transistors
can be made smaller, increasing transistor density by approximately two times.
When the hafnium ceramic is combined with a compatible metal gate, the result is more than
a 20 percent increase in drive current (higher transistor performance) and more than a five
times reduction in source-drain leakage, thus improving the energy efficiency of the
transistor. The smaller transistor size means active switching power is reduced by
approximately 30 percent.
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Hip Replacements Become Stronger with Ceramic femoral head and acetabular cup
Over the last twenty years there has been a considerable increase in the use of ceramic
materials for implant devices. With an excellent combination of strength and toughness
together with bio-inert/biocompatible properties and low wear rates, special type of oxide
ceramics called zirconia and alumina are currently used for applications such as femoral
heads and acetabular cups for total hip replacements.
The zirconia heads have double the strength of comparable alumina heads and consequently
the diameter of the femoral head can be reduced to < 26 mm, leading to a reduction in patient
trauma during the hip replacement operation. Other applications for zirconia implants include
knee joints, shoulders, phalangeal joints and spinal implants. This material is also being used
for endoscopic components and pace maker covers.
Ceramic Coatings for Drug Release
MIV Therapeutics, Inc., a leading developer of new generation biocompatible coatings and
advanced drug delivery systems for cardiovascular stents and other implantable medical
devices, is developing coatings based on hydroxyapatite (HAp), a ceramic material that has a
similar composition to natural bone. These proprietary coatings show potential for
outperforming technologies and products currently in use that release drugs after stent
implantation. The microporous films are designed to remain highly biocompatible even after
all drug material is eluted from the coating. In this respect, HAp performance far exceeds
polymer-based coatings, wherein drugs are necessary to sustain acceptable coating
performance.
The ultra-thin films are designated as a surface modification of metallic implants, whereas the
micro-thin films are evaluated also as a potential vehicle for drug delivery purposes for
implantable medical devices. In the extremely demanding application on stents the coating
not only has to withstand deformation during manufacturing (i.e. stent crimping) and at the
implantation stage and remain un-damaged in such operation. If this was not enough, the
coating has to maintain its integrity and resist fatigue stresses in concert with the heart beat
over the years after deployment in human heart.
Composite Layers for Gene Therapy
An efficient and safe gene transferring system is a key technology in gene therapy and tissue
engineering. Particles of DNA/calcium phosphate complex have long been used for
facilitating gene transfer because of their low toxicity. The gene transferring efficiency of this
reagent is, however, insufficient compared with other reagents such as DNA/lipid complexes.
Recent research has shown that gene transfer on the surface of a DNA/apatite composite layer
is as efficient as an optimized commercial lipid-based reagent.
A laminin/DNA/apatite composite layer was successfully formed on the surface of an
ethylene/vinyl alcohol copolymer by Japanese researchers. The immobilized DNA was
transferred to the cells adhering onto the laminin/DNA/apatite composite layer more
efficiently than those adhering onto a laminin-free/DNA/apatite composite layer. It is
considered that laminin immobilized in the surface layer enhances cell adhesion and
spreading, and DNA locally released from the layer is effectively transferred into the
adhering cells, taking advantage of the large contact area. The present gene transferring
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system, which shows high efficiency and safety, would be useful in gene therapy and tissue
engineering.
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Silicon nitride (a non-oxide ceramic) is used as radomes for missiles in the latest air defense
systems. It was specifically selected for missile radomes because of its mechanical strength
and dielectric properties. The material allows microwave or other energy to pass through to
locate incoming targets. Its mechanical strength allows the missile system to withstand
erosion and large temperature excursions while flying at hyper-velocity through the
atmosphere. Also under development are transparent infrared windows using nanocrystalline
yttria (a type of oxide ceramic) for missile applications.
Improved glasses and glass ceramics are also being considered for armor windows with the
desired ballistic performance. Glasses can be produced in large sizes with curved geometries,
and can be produced to provide incremental ballistic performance at incremental cost. A
fused silica glass is one material under development.
Other transparent materials are being considered for windshields, blast shields, and sensor
protection in aircraft. A ceramic material called spinel (magnesium aluminate) has superior
optical properties within the infrared region, which makes it attractive in sensor applications
where effective communication is impacted by the protective domes absorption
characteristics.
Improving Turbine Engine Efficiency
Future Army helicopters will be able to fly farther and carry more payload thanks to
ceramics. Turbine engine operational efficiencies can be increased through the use of ceramic
matrix composites and ceramic thermal barrier coatings due to their high temperature
capability. Ceramics have the potential to operate at temperatures above 1100C with
minimal or no cooling. Composites are also 30 to 50% lighter than the metallic alloys
currently in use. When composite combustor liner and turbine vane applications are coated
with ceramics, operating temperatures increase to 1650C and the components are protected
from the combustion environment. A multi-component ceramic coating based on hafnium
oxide has survived a 300 hour test at 1650C.
shoes. The same type of lightweight ceramic textile used to protect space shuttle tiles, 3Ms
Nextel, is being used as thermal barriers for the transmission/tunnel, header/collector, spark
plug boots, drivers floor panel and firewall. Nextel ceramic textiles maintain their strength
and flexibility at continuous temperatures in excess of 2000F and help keep race car cockpit
surfaces 40 percent cooler.
Make a Birdie with Ceramic Putters
High performance ceramic materials are helping to shave strokes off a golfers handicap.
Ceramics are the perfect material for a putter head because it is lighter and softer than steel
and provides increased feel and control. Despite its lightness, ceramic materials have a
reputation for durability and toughness. When made of a solid one-piece construction,
ceramic putters provide one huge sweet spot, which translates into more successful putts
and better consistency.
Skiing Smarter With Piezoelectric Fibers
Used by reputable ski manufacturers, revolutionary ceramic disc technology developed by
Norton Industries is achieving the sharpest, smoothest ground edge while providing a near
mirror finish for skis. Thus, skis and snowboards turn and grip icy slopes better, improving
both performance and safety. Edges also remain sharper longer.
Head Sport, a leading sports equipment manufacturer, is also manufacturing smart skis that
make use of a ceramics piezoelectric properties. When skiing at high speeds, skis tend to
vibrate, lessening the contact area between the ski edge and snow surface. This results in
reduced stability and control and decreases the skiers speed.
The skis are embedded with piezoelectric fiber composites developed by Advanced
Cerametrics. These composites convert the unwanted vibrations into electrical energy, thus
keeping the skis on the snow. The skis continuously adjust to all conditions, with a maximum
reaction time of 5 thousandths of a second. Ceramic fiber technology also guarantees up to
6% more functional edge, helping several athletes at the 2006 Winter Olympics win two gold
medals and one silver. The skis are available at high end sporting goods stores and have been
the choice of ski instructors and ski patrollers for three years. The skis were one of Time
Magazines Coolest Products for 2002and won the 2003 R&D 100 Award.
Such ceramic fibers have two important qualities: on the one hand they feature exceptional
wear resistance and on the other they have far better torsional properties than many plastic
materials. However, the main advantage of ceramic fibers is their ability to change shape very
slightly when subjected to small electrical charges.
Advanced Cerametrics fibers are also used in several of Heads tennis rackets, adding up to
15% more power to a ball hit. The Intelligence, Protector and LiquidMetal lines of rackets
using these piezo ceramic fibers were the largest selling rackets in the world in the 2005/2006
season. They have been clinically proven to eliminate tennis elbow. The Protector racket was
also selected 2005 Racket of the Year by Tennis Magazine. In the summer of 2006, smart
pool cues made with these fibers (JossWest made by Hamson Industries) won the largest
purse ever in a pool tournament.
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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
silicatesthat is, compounds based on silica (SiO2 ), and 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
micrometre size. When these particles are suspended in or mixed with water, the mixture
exhibits unusual rheology, or flow under pressure. This behaviour 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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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.
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.
Processing
Beneficiation
Compared with other manufacturing industries, far less mineral beneficiation (e.g., washing,
concentrating, sizing of particulates) is employed for silicate ceramics. Clays going into
common structural brick and tile are often processed directly as dug out of the ground,
although there may be some blending, aging, and tempering for uniform distribution in water.
Such impure clays are workable in untreated form because they already contain fillers and
fluxes in association with the clay minerals. In the case of whitewares, for which the raw
materials must be in a purer state, the clays are washed, and impurities are either settled out
or floated off. Silicas are purified by washing and separating unwanted minerals by gravity
and by magnetic and electrostatic means. Feldspars are beneficiated by flotation separation,
a process in which a frothing agent is added to separate the desired material from impurities.
Blending
The calculation of amounts, weighing, and initial blending of raw materials prior to forming
operations is known as batching. Batching has always constituted much of the art of the
ceramic technologist. Formulas are traditionally jealously guarded secrets, involving the
selection of raw materials that confer the desired working characteristics and responses to
firing and that yield the sought-after character and properties. Clays must be selected on the
basis of workability, fusibility, fired colour, and other requirements. Silicas, likewise, must
meet criteria of chemical purity and particle size distribution.
Forming
The fine, platy morphology of clay particles is used to advantage in the forming of clay-based
ceramic products. Depending upon the amount of water added, clay-water bodies can be stiff
or plastic. Plasticity arises by virtue of the plate-shaped clay particles slipping over one
another during flow. (Nonclay ceramics can be similarly formed if plasticizersusually
polymersare added to their mixes. In many cases organic binders are used to help hold the
body together until it is fired.) With even higher water content and the addition of dispersing
agents to keep the clay particles in suspension, readily flowable suspensions can be produced.
These suspensions are called slips or slurries and are employed in the slip casting of clay
bodies. The mechanisms of plastic forming and slip casting are described below.
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Plastic forming
Plastic forming is the primary means of shaping clay-based ceramics. After the raw materials
are mixed and blended into a stiff mud or plastic mix, a variety of forming techniques are
employed to produce useful shapes, depending upon the ceramic involved and the type of
product desired. Foremost among these techniques are pressing and extrusion.
Pressing involves the application of pressure to eliminate porosity and achieve a specific
shape, depending upon the die employed. Refractory bricks, for example, are often made by
die presses that are either single-action (pressing from the top only) or dual-action
(simultaneously pressing from top and bottom). Structural clay products such as brick and tile
can be made in the same fashion. In pressing operations the feed material tends to have a
lower water content and is referred to as a stiff mud.
The problem with die casting is that it is a piecemeal rather than a continuous process,
thereby limiting throughput. Many silicate ceramics are therefore manufactured by extrusion,
a process that allows a more efficient continuous production. In a commercial screw-type
extruder, a screw auger continuously forces the plastic feed material through an orifice or die,
resulting in simple shapes such as cylindrical rods and pipes, rectangular solid and hollow
bars, and long plates. These shapes can be cut upon extrusion into shorter pieces for bricks
and tiles.
Slip casting
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As mentioned above, with sufficient water content and the addition of suitable dispersing agents,
clay-water mixtures can be made into suspensions called slurries or slips. These highly stable
suspensions of clay particles in water arise from the careful manipulation of surface charges on the
platelike clay particles. Without a dispersing agent, oppositely charged edges and surfaces of the
particles would attract, leading to flocculation, a process in which groups of particles coagulate into
flocs with a characteristic house-of-cards structure. Dispersing agents neutralize some of the surface
charges, so that the particles can be made to repel one another and remain in suspension indefinitely.
When the suspension is poured into a porous plaster mold, capillary forces suck the water into the
mold from the slip and cause a steady deposition of clay particles, in dense face-to-face packing, on
the inside surface of the mold. After a sufficient thickness of deposit has been obtained, the remaining
slip can be poured off or drained and the mold opened to reveal a freestanding clay piece that can be
dried and fired. Surprisingly complex shapes can be achieved through slip casting.
Firing
After careful drying to remove evaporable water, clay-based ceramics undergo gradual heating to
remove structural water, to decompose and burn off any organic binders used in forming, and to
achieve consolidation of the ware. Batches of specialty products, produced in smaller volumes, are
cycled up and down in so-called batch furnaces. Most mass-produced traditional ceramics, on the
other hand, are fired in tunnel kilns. These consist of continuous conveyor belt or railcar operations,
with the ware traversing the kiln and gradually being heated from room temperature, through a hot
zone, and back down to room temperature. Pyrometric cones, which deform and sag at specific
temperatures, often ride with the ware to monitor the highest temperature seen in the traverse through
the kiln.
Vitrification
The ultimate purpose of firing is to achieve some measure of bonding of the particles (for strength)
and consolidation or reduction in porosity (e.g., for impermeability to fluids). In silicate-based
ceramics, bonding and consolidation are accomplished by partial vitrification. Vitrification is the
formation of glass, accomplished in this case through the melting of crystalline silicate compounds
into the amorphous, noncrystalline atomic structure associated with glass. As the formed ware is
heated in the kiln, the clay component turns into progressively larger amounts of glass. The partial
vitrification process can be analyzed through a phase diagram such as that shown in Figure 2.
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In this diagram three crystalline phases are shown: the end members cristobalite (one
crystallographic form of silica [SiO2]) and alumina (Al2O3) and an intermediate compound,
mullite (3Al2 O3 2SiO2). The melting points of alumina and cristobalite, as shown on the left
and right edges of the diagram, are quite high. However, intermediate compositions begin to
melt at lower temperatures. As shown by the two horizontal lines on the diagram, melting
begins to occur at 1,828 C (3,322 F) for high alumina compositions and as low as 1,587 C
(2,889 F) for high silica compositions. (These temperatures can be lowered still further by
the addition of fluxing agents, such as alkali or alkaline-earth oxide feldspars.) Between the
two horizontal lines and the region of the diagram marked liquid, all compositions are only
partly liquid (e.g., mullite and liquid, alumina and liquid). This partial vitrification allows for
the retention of solid particles, which helps to maintain the rigidity of the ceramic piece
during firing in order to minimize sagging or warpage.
The role of the glassy liquid phase in the consolidation of fired clay objects is to facilitate
liquid-phase or reactive-liquid sintering. In these processes the liquid first brings about a
denser rearrangement of particles by viscous flow. Second, through solution-precipitation of
the solid phases, small particles and surfaces of larger particles dissolve and reprecipitate at
the growing necks that connect large particles. Rearrangement and solution-precipitation
lead to bond formation and to progressive densification with reduction of porosity. A range of
glass contents and residual porosities can be obtained, depending on the ingredients and the
time the object is held at maximum temperature.
Finishing
If fired ceramic ware is porous and fluid impermeability is desired, or if a purely decorative
finish is desired, the product can be glazed. In glazing, a glass-forming formulation is
pulverized and suspended in an appropriate solvent. The fired ceramic body is dipped in or
painted with the glazing slurry, and it is refired at a temperature that is lower than its initial
firing temperature but high enough to vitrify the glaze formulation. Glazes can be coloured
by the addition of specific transition-metal or rare-earth elements to the glaze glass or by the
suspension of finely divided ceramic particles in the glaze.
Products
The raw materials and manufacturing processes outlined above produce a range of traditional
ceramic products. These products are described in some detail in separate articles on
whiteware, structural clay products, brick and tile, refractory, abrasive, and cement.
Further Reading
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