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10% Whiteware
9% Porcelain enamel
7% Refractories
2% Structural clay
Overall market distribution in the United States is as
follows:
32% Flat glass
18% Lighting
17% Containers
9% TV tubes, CRTs
5% Consumer glassware
1% Technical/laboratory
1% Other
Advanced ceramics form the second largest sector of the
industry.
More than half of this sector is electrical and electronic
ceramics and ceramic packages:
36% Capacitors/substrates/packages
23% Other electrical/electronic ceramics
13% Other
12% Electrical porcelain
8% Engineering ceramics
8% Optical fibers
General properties
The constituent atoms in a ceramic are held together by very strong
bonding forces which may be ionic, covalent or a mixture of the two.
Their melting points are often very high, making them eminently suited for
use in energy-intensive systems such as industrial furnaces and gas turbines.
For instance, alumina primarily owes its importance as a furnace refractory
material to its melting point of 2050oC.
The valence electrons are tied up in bonds, and are not free as they are
in metals. In metals it is the free electrons—the electron gas—that
determines many of their electrical and thermal properties.
resistivity below 92 K.
Many ceramics are transparent because
However, it is the combination of low density with this stiffness that makes
ceramics particularly attractive for structures in which weight reduction is a
prime consideration.
The strong inter atomic bonding means that ceramics are hard as well
as strong. That is, they resist penetration by scratching or indentation
and are potentially suited for use as wear-resistant bearings and as
abrasive particles for metal removal
Generally, impact conditions should be avoided. Interestingly, shape can
influence performance; thus, the curved edges of dinner plates are carefully
designed to maximize resistance to chipping.
The final porosity, by volume, of the fired material ranges from 30% to
nearly zero.
Together with grain size, it has a direct influence upon the modulus of
rupture; thus, bone china, because of its finer texture, is twice as strong as
fired earthenware.
machine jigs
cutting tools
tape-recording machines
grinding abrasives
Oxide Ceramics
Oxidation resistant, chemically inert, electrically insulating,
generally low thermal conductivity, slightly complex
manufacturing and low cost for alumina, more complex
manufacturing and higher cost for zirconia.
Non-Oxide Ceramics
Low oxidation resistance, extreme hardness, chemically inert,
high thermal conductivity, and electrically conducting,
difficult energy dependent manufacturing and high cost.
Classification
Pottery
Heavy clay products(bricks, earthenware pipes, etc.)
Refractories (firebricks,silica, alumina, basic, neutral), cement and
concrete, glasses and vitreous enamels
Engineering(technical,fine) ceramics
Very high strength
Hardness
Plasticisers and binders are blended with these powders to suit the
preferred method of forming (pressing, extrusion, slip casting, etc.) to
produce the “raw” material.
Both high and low-pressure forming techniques are used. The raw
material is formed into the required “green” shape or precursor
(machined or turned to shape if required) and fired to high
temperatures in air or a slightly reducing atmosphere to produce a
dense product.
Non-Oxide Ceramics processing
Water jet
Diamond cutting
Diamond grinding
Drilling
The atomic bonding in these materials ranges from purely ionic to totally
covalent; many ceramics exhibit a combination of these two bonding types
For those ceramic materials for which the atomic bonding is predominantly
ionic, the crystal structures may be thought of as being composed of
electrically charged ions instead of atoms.
The metallic ions, or cations, are positively charged, because they have given
up their valence electrons to the nonmetallic ions, or anions, which are
negatively charged.
AX-Type Crystal Structures
Some of the common ceramic materials are those
in which there are equal numbers of cations and
anions. These are often referred to as AX
compounds, where
A denotes the cation and X the anion.
It is also possible for ceramic compounds to have more than one type of
cation;for two types of cations (represented by A and B), their chemical
formula may be designated as AmBnXp .
Barium titanate (BaTiO3), having both Ba 2+ and Ti 4+ cations, falls into this
classification. This material has a perovskite crystal structure
Structural ceramics
Include silicon nitride (Si3N4), silicon carbide (SiC), zirconia (ZrO2),
boron carbide (B4C), and alumina (Al2O3).
They are used in applications such as cutting tools, wear components,
heat exchangers, and engine parts.
Their relevant properties are high hardness, low density, high-
temperature mechanical strength, creep resistance, corrosion resistance,
and chemical inertness.
There are three key issues to solve in order to expand the use of
structural ceramics:
Reducing cost of the final product
Improving reliability
Improving reproducibility
Electronic ceramics
Include barium titanate (BaTiO3), zinc oxide (ZnO), lead
zirconate titanate [Pb(ZrxTi1−x)O3], aluminum nitride
(AlN), and HTSCs.
They are used in applications as diverse as capacitor
dielectrics, varistors, microelectromechanical systems
(MEMS), substrates, and packages for integrated circuits.
There are many challenges for the future:
Integrating with existing semiconductor technology
Improving processing
Solution
Vaporization
Types Of Powders
Primary particles are the smallest clearly identifiable unit in the powder. Primary
particles may be crystalline or amorphous and cannot easily be broken down into
smaller units.
Agglomerates are clusters of bonded primary particles. Soft agglomerates are easily
broken up; hard agglomerates, because of the stronger interparticle bonds, are more
difficult to break up. Hard agglomerates should be avoided in ceramic powder
processing as much as possible.
Colloids are very fine particles (they can be as small as 1 nm in diameter) held in
fluid suspension by Brownian motion. consequently, colloidal particles will
settle very slowly.
Aggregates are coarse constituents, >1 mm, in a mixture. The important example
is the addition of gravel to cement to make concrete. In early concrete structures
MECHANICAL MILLING
Solid-state reaction
Involves high temperatures.
The hydroxide particles precipitated from the sol are spherical, uniform
in shape and sub-micron sized.
Reaction 1: Hydrolysis
(C3H7O) 2–Al–OC3H7 + HOH →(C3H7O) 2–Al–OH +
C3H7OH
Reaction 2: Condensation
(C3H7O) 2–Al–OH + C3H7O–Al–(C3H7O)2 → (C3H7O)
Amongst the oxide ceramics, alumina, Al2O3, is the most commonly used ceramic
High hardness
Wear resistance
High modulus
Inertness
Refractoriness
chemical resistance,
smooth surface
reasonable strength
moderate thermal conductivity
Low electrical conductivity insulators- spark plugs in automotive and aircraft engines
during World War II
Alumina ceramics are the most widely used oxide-type ceramic, chiefly
because alumina is plentiful, relatively low-cost, and equal to or better than
most oxides in mechanical properties.
Density can be varied over a wide range, as can purity—down to about 90%
alumina— to meet specific application requirements. Alumina ceramics are
the hardest, strongest, and stiffest of the oxides.
They are also outstanding in electrical resistivity and dielectric strength, are
resistant to a wide variety of chemicals, and are unaffected by air, water
vapor, and sulfurous atmospheres.
However, with a melting point of only 3700°F (2037°C), they are relatively
low in refractoriness, and at 2500°F (1371°C), retain only about 10% of
room-temperature strength.
In addition to alumina’s wide use as electrical insulators and in chemical
Units Property/ Material Alumina
% Alumina 85 90 92 96 97 I 98 99.5
1000psi Tensile 18 26 28 30 30 30 32
1000psi Flexural 45 52 55 55 55 55 60
- Porosity 0 0 0 0 0 0 0
Thermal
g.cal/cm-sec-ºC 0.042 0.044 0.045 0.049 0.050 0.052 0.055
Conductivity
in/inºCx10-7 C.T.E. 67 70 71 75 76 77 78
ºC Max. Working Temp. 1350 1400 1500 1600 1650 1650 1700
D.C.Volts/Mil. @ 0.100"
Dielectric Strength 190 210 210 230 230 240 250
thick
Ohm/cm3x 1012 Volume Resistivity 0.02 0.5 1.0 2.0 3.1 3.2 3.5
http://www.gbcmaterials.com/mat_alumina.htm
Properties Condition Units 960P 975P 998P 96S IP-95 IP-99
Mechanical
Interatomic bonding forces, partly ionic and partly covalent, are extremely
strong and the crystal structure of alumina is physically stable up to
temperatures of 1500-17000C.
Additions of oxides such as SiO2, CaO and MgO which act as fluxes,
forming a fluid glassy phase between the grains of a-alumina during
sintering.
Sip- or tape-casting
Roll-forming
Extrusion
Injection moulding
In some processes, binders are incorporated with the powder; for instance, a
thermoplastic can be hot-mixed with alumina powder to facilitate injection-
moulding and later burned off.
The matter of our attention were additives from the CaO-MgO-SiO2 and
CaO-SiO2 system, which should assure coarse grain ceramics with high
dielectric strength
'Harder' firing incurs heavier energy costs and has led to the development of
reactive alumina which has an extremely small particle size (1 um) and a
large specific surface.
'Softer' firing temperatures became possible with this grade of alumina and
the need to debase the alumina with relatively large amounts of additives
was challenged.
Investigations indicated an influence of additive composition on
microstructure development. An effect of addition of small amounts of
MgO on alumina microstructure is well known.
The powder is condensed within a carrier gas and then separated from the
gas stream by impingement filters or electrostatic precipitators. Sometimes,
in a chemical vapour deposition process (CVD), a thin film is condensed
directly upon a substrate.
Alumina has low fracture toughness but it can be considerably improved by
making a composite in which fine particles of zirconia (ZrO2) are uniformly
dispersed .
For abrasives, the grain sizes are usually from 100 to 600 mesh.
The larger grain sizes are made up of many crystals, unlike the
singlecrystal large grains of silicon carbide.
Type A is alpha alumina with hexagonal crystals of particle size 11.8
in (0.3 m), specific gravity 4.0, and Mohs hardness 9.
The aluminum oxide abrasives in all forms are sold under trade names.
Alundum, of Saint-Gobain Industrial Ceramics, formerly Norton
Materials; Aloxite, of Carborundum Co; and Lionite, of General
Abrasives are aluminum oxides
Alumina ceramics are finding increasing use in applications such as pump
seals, wear plates for industrial components, sand blast nozzles, extrusion
dies, etc.
Like silicon nitride, silicon carbide is a family of materials each with its sp
ecial characteristics. Most of the silicon carbide materials have very high h
ardness (harder than alumina and silicon nitride) and thus have superior we
ar resistance.
Most have unusually high thermal conductivity for a ceramic, low thermal
expansion compared to metals, and very high temperature capability.
In situ reaction
Reaction bonding
Sintering
In situ reaction
In the first method a carbon tube is heated to about 1900°C in a bed of
sand (SiO2) and coke (C).
The SiC tube is then removed and the residual carbon is burnt out. The
tube has a porosity of about 30% and a large internal surface area.
To prevent internal oxidation during use, the outer surfaces of the tube
are coated with a thin layer of a calcium aluminosilicate glass and are
then fired at about 1450°C.
Reaction bonding
In the second method a mix of SiC and carbon powders and a polymer
binder is extruded to a rod. The “green” form is then brought in contact
with molten silicon.
The liquid penetrates the pores reacting with the carbon to form silicon
carbide and bonding the grains together.
To give the rod low-resistance terminations, the ends are dipped into
molten silicon, which is allowed to infiltrate along a predetermined
length.
In all cases the ends of the elements are coated with aluminum to make
electrical contacts.
Bearings,
Turbocharger rotors,
Although silicon nitride bearings are still 2–5 times more expensive than the
best bearing steel, their superior performance and life
have resulted in rapid escalation in their use.
One of the most important applications of silicon nitride bearings is
tool spindles Because of their light weight (60% lighter than steel),
silicon nitride bearings can be operated at much higher speed than metal beari
ngs without generating a critical level of centrifugal stress.
Because of their low thermal expansion (one-fifth that of steel) and high elastic
modulus, the silicon nitride bearings can operate to much closer tolerances t
han metal bearings, which enables machines
with higher precision and lower vibration.
Because of their high hardness and smoother surface, the silicon nitride bearin
gs run smoother and wear at about one-seventh the rate
of the best metal bearings.
All of these factors together result in 3–10 times the life of metal
bearings, up to 80% higher speed capability, about 80% lower
friction, higher operating temperature, and 15–20% reduction in
energy consumption.
In addition to cutting tool inserts, bearings and check
valves, silicon nitride is being vigorously evaluated for
Silicon nitride exists in two crystalline forms (a, b): both belong to the
hexagonal system.
Die-pressing
Isostatic-pressing
Slip-casting
Flame-spraying
Polymer-assisted injection-moulding
Extrusion
In the first stage of a reaction-bonding process, this pre-form is heated in a
nitrogen atmosphere and the following chemical reaction takes place
Single crystal 'whiskers' of a-silicon nitride also nucleate and grow into pore
space.
Each form is isostructural with one of the two common forms of Si3N4,
beta (β) and alpha (α) and with silicon oxynitride.
The tetrahedra are linked together into a rigid three dimensional framework
by sharing corners. The Si-N bonds are short and they are very strong. This
strong, rigid, compact structure is responsible for many of the important
properties of Si3N4.
β-Sialon
They have good refractory properties, they are low in strength and
toughness and therefore are not bracketed as advanced ceramics.
corrosion
Stabilized zirconia is used as a grinding media and engineering ceramics due to its
increased hardness and high thermal shock resistivity.
Stabilized zirconia is also used in applications such as oxygen sensors and solid oxide
fuel cells due to its high oxygen ion conductivity.
Unstabilized (Pure) Zirconia
The pure zirconia particles in PSZ can metastabily retain the high-
temperature tetragonal phase.
Sintering:
Room Temperature ® 900° C 2° C/min.
900° C ® 1300° C 1° C/min.
1300° C ® 1540° C 2° C/min.
1540° C Keep 2 hours
1540° C ® 1000° C 2° C/min.
1000° C ® Room Temperature Stop heating and keep in furnace.
The properties of fired PSZ:
Density: 5.95-6.05 g/cm3
HRA: 89 Sore D
Flexural Strength: 940 MPa
In late 1929, Ruff and co-workers demonstrated the possibility of
stabilization of C-phase at room temp by adding small amount of
CaO. The addition of stabilizing oxides, like CaO, MgO, CeO2, and
Y2O3, to pure Zirconia allows generating multi phase materials
known as Partially Stabilized Zirconia (PSZ).
T-M phase transformation in partially stabilized Zirconium (PSZ)
and in the process improves the mechanical and physical properties
of the material.
Tetragonal (T) phase of PSZ is in metastable state at room
temperature. The state is metastable because the transformation from
T to M phase can be induced by external influence like tension or
temperature.
On PSZ, when tensile stresses acting at the crack tip induces
transformation of metastable T phase to M phase. This
transformation is associated with local increase of 3 % to 5 % in
volume.
This increase in volume results in localized compressive stresses
being generated around and at the crack tip. Thereby squeezing the
crack. This physical property is known as transformation toughening.
Transformation-toughened Zirconia
The tetragonal grains are the ones that transform adjacent to a crack.
A crack in a normal ceramic travels all the way through the ceramic with
little inhibition, resulting in immediate fracture. TTZ has fracture toughn
ess (resistance to crack propagation) three to six times higher than norma
l zirconia and most other ceramics. It is tougher than cast-iron and comparabl
e in toughness to some compositions of WC–Co cermet.
Table 2.5 lists some of the applications where TTZ has been s
uccessful.
Filters for molten metals often have pore sizes of 300–800 μm,
whereas membranes for reverse osmosis have pore sizes of a few
tenths of a nanometre.
Different techniques for creating porous bodies. The choice of technique
depends on the desired structure and pore size. One of the techniques is based
on the foaming of a powder/protein suspension. Porosities between 50 and
80% with pore sizes in the range 10–500 μm have been obtained.
The addition of a fugitive agent is another method of providing porosity in a
ceramic material. The total porosity and pore size distribution can be carefully
controlled by the choice of fugitive agent and the amount added. This method
results in both open and closed pores depending on the total porosity.
Laminated structures with, e.g. alternating dense and porous layers or a
gradient structure with increasing pore sizes can easily be created using the
technique of adding a fugitive resin. Porosity can also be created by controlling
the particle interaction.
The choice of powder, particle size, packing technique and sintering procedure
determine the final structure. All of the above mentioned techniques allow the
forming of complex shapes.
As an example it can be mentioned that porous materials with more
than 90 vol% porosity for thermal insulation has been developed with
extremely low thermal conductivity (< 0.08 W/m K).
Ultrafiltration membranes built up of three layers are another result of
our efforts in the field of porous structures.
The ultrafiltration membrane top layer has pore sizes as small as 6 nm.
The characterisation of porosity and pore sizes by water intrusion,
mercury intrusion and scanning electron microscopy are services
frequently used in the development of porous structures.
Laminated intermediate layer and support sintered at 1200 oC
with a dip-coated top layer.
Glass ceramic
There are materials that are hybrids between glasses and ceramics.
They are nonporous and are either opaque or transparent. Their optical
transparency arises from the fact that the crystals are smaller than the
wavelength of visible light such that the light waves are transmitted without
significant scattering.
Like glasses, glass ceramics have excellent corrosion and oxidation resistance,
but have improved impact strength and dimensional stability over both glasses
and ceramics.
Glass ceramics are commonly made of compositions in the MgO–
Al2O3–SiO2, and Li2O–Al2O3–SiO2 systems, with the main crystal
phases being cordierite (Mg2Al4Si5O18) and β-quartz and β-
spudomene (Li2O.Al2O3 .4SiO2) solid solutions.
The residual glass phase is usually 1–10% by volume.
In the first stage, which can begin while the glass is cooling from the
forming and shaping operation, holding at a specific temperature for a
definite time period causes the catalyst to initiate the precipitation of large
numbers of nuclei throughout the glassy matrix.
When these seed regions reach a certain size, different species of crystals
may begin to grow upon them.
Certain oxides could also act as effective nucleating agents and led to
development of the first glass-ceramics, which were based on the SiO2-
Al2O3-LiO2system.
Volatilization and interaction between the melt and the refractory lining of
the melting furnace can make this difficult.
For instance, high proportions of lithium oxide in the melt will increase
attack on the lining.
Although conventional glasses have a useful
'long‘ range of temperature over which they can be
worked, the composition of potential glass-
ceramics restricts ('shortens') this range,
particularly when aluminium oxide is present.
For instance, glass-ceramic hob plates for electric cookers are strong,
smooth and easy to clean, stable over long periods of heating, transparent
to infrared radiation from the tungsten halogen lamp, relatively opaque to
visible light (reducing glare) and resistant to thermal shock. The last
property originates primarily from the low thermal coefficient of thermal
expansion (a) of this particular glass-ceramic.
Careful balancing of their relative amounts against the residual glass content can
reduce the overall expansion coefficient towards zero.
This capability is ideal for the large mirror blanks used for telescopes where dime
nsional stability is essential.
In heat engines such as lorry gas turbines, a low expansion coefficient is required
for the regenerative heat exchanger which is alternately heated and cooled by exh
aust gases and combustion air. In glass/glass and metal/glass seals, precise matchi
ng of expansion characteristics is possible.
It is well-known that the fluxing oxides of sodium and potassium lower the
chemical resistance of silica glass to aqueous solutions; in glass-ceramics,
this susceptibility is countered by stabilizing any residual glass phase with
boric oxide.
Attempts are being made to extend their use to much higher temperatures
(e.g. 1300-170O0C) by exploiting refractory systems, such as SiO2-Al2O3-
BaO, which can provide a liquidus temperature above 175O0C but such
glasses are very difficult to melt.
Conversion from glass to crystals causes mobile ions to disappear from
the structure and become 'bound‘ to crystals, consequently the electrical
resistivity and dielectric breakdown strength of glass-ceramics are high,
even at temperatures up to 500-70O0C. The dielectric loss is low.
Utilization of plentiful and cheap waste byproducts from industry for the
bulk production of glass-ceramics has stimulated much interest.
The two most common chemical bonds for ceramic materials are covalent
and ionic. The bonding of atoms together is much stronger in covalent and
ionic bonding than in metallic.
The top schematic drawing illustrates tape casting. The bottom sketch shows
the different stages during the processing: the slip consisting of water, ceramic
particles and binder; the cast, dried green sheet; and, finally, the microstructure
of the sintered material.
Tape Casting
This process involves the casting of a slurry onto a flat moving carrier
surface. The slurry usually consists of a ceramic powder with the
appropriate additions of solvents plasticisers and binders.
The slurry passes beneath the knife edge as the carrier surface
advances along a supporting table. The solvents evaporate to leave a
relatively dense flexible sheet that may be stored on rolls or stripped
from the carrier in a continuous process.
"As-Cast" Tape Cast Strip
Tape casting is a forming technique for producing thin, flat ceramics. The
method was originally deve-loped for producing electronic ceramics
(insulating substrates and packages and multilayer capacitors) and is still
mainly used for this. Structural laminates, knives, membranes and solid
oxide fuel cells are examples of other applications for thin ceramics formed
by tape casting. The tape thickness that can be achieved is generally in the
range of 25 μm up to 1 mm but it is possible to produce tapes down to 5 μm.
The Swedish Ceramic Institute (SCI) has focused its research and
development within this area on water-based tape casting. An aqueous
system has the advantages of reducing health and environmental hazards
coupled with lower cost and a more manageable process. Among the
disadvantages of water-based tape casting we can mention slower drying,
higher crack sensitivity and, for some ceramics, reactions with water.
Studies have been made, in which the SlipGreen TapeSintered
MaterialTape CastingBurn-out,SinteringCast TapeCasting BladeSlipCarrier
Film entire process chain has been evaluated with regard to rheological
properties, drying, binder removal, sintering and, finally, microstructure.
Acrylic latex-type binders have been identified as the best type of binder
owing to their low viscosity at high polymeric content and their internal
plasticization, which makes additional plasticizer superfluous. Furthermore,
lamination is possible at room temperature. Green tapes are obtained that are
insensitive to air humidity, at the same time as they have a high quality with
regard to surface smoothness, flexibility and green density. The longer drying
times of water-based systems are overcome by the fact that higher solids
loading is possible in aqueous systems than in organic, solvent-based systems,
coupled with effective heating during drying. Important characteristics of the
latex relevant to the processing are the latex particle size, the stabilisation
type of the latex and the type of polymer.
So far, SCI has tape cast the following materials: Al2O3, ZrO2, cordierite,
mullite, alu minium titanate, PZT, SiC, Si3N4 and particulate composite
materials: Al2O3-ZrO2, cordierite-ZrO2 and Si3N4-TiN. Laminated
structures such as Al2O3 membranes, SiC/C laminates and PZT-actuators
have been made of these materials. SCI’s tape caster (TC 155 from AEM Inc.)
is a continuous machine with a stationary casting head. The machine is
designed for making thin tapes with a thickness range 4–400 μm. For thicker
com ponents (0.5 mm up to 7 mm) lamina tion of green tapes is possible.
Diamond Grinding
High levels of accuracy and surface finish can be achieved
by diamond grinding. Tolerances of a few microns are
commonplace. However, diamond grinding is a relatively
expensive micro-machining process, consequently, if a
design can be produced to "as-fired" tolerances, the overall
cost of the component is reduced. Precision Machining
(Diamond Grinding) of Engineering Ceramics
Source “ Manufacturing Processes for Engineering Materials”, 4th edition, Kalpakjian, Schmid,
Prentice Hall 2003
Figure from: “ Manufacturing Processes for Engineering Materials”, 4th edition,
Kalpakjian, Schmid, Prentice Hall 2003