An Introduction to Ceramic Materials

Content
What are ceramics?
Types of ceramics
Structure and bonding
Properties of ceramics
Processing of ceramics
Applications
Modern trends

The Word Ceramics

Greek term = Keramos = Pottery
Going back from Greek. The Greek took this word from older Sanskrit root meaning
�to burn�
Thus the Greeks used this word to mean �burned stuff� or �burned earth�
Defining Ceramics Materials
Ceramics encompass such a vast array of materials that a concise definition is
almost impossible.
One workable definition of ceramics is a refractory, inorganic, and nonmetallic
material. It can also be defined as products made from inorganic materials having
non-metallic properties, usually processed at a high temperature at some time
during their manufacture.
The American Society for Testing and Materials (ASTM) defines a ceramic article as
�an article having a glazed or unglazed body of crystalline or partly crystalline
structure, or of glass, which body is produced from essentially inorganic, non-
metallic substances and either is formed from a molten mass which solidifies on
cooling, or is formed and simultaneously or subsequently matured by the action of
the heat.�
Examples
So generally speaking almost all the carbides, borides, oxides and nitrides are
ceramic materials.

Carbides: SiC, WC etc

Nitrides: Si3N4, TiN etc
Oxides: SiO2, Al2O3, MgO etc
Borides: TiB2, MgB2, MgB4 etc

Types of Ceramics
Ceramics can be divided into two classes:

Traditional Ceramics
Engineering Ceramics

Traditional Ceramics:
Traditional ceramics include clay products, silicate glass and
cement

Engineering Ceramics:
They consist of carbides (SiC), pure oxides (Al2O3), nitrides
(Si3N4), non-silicate glasses and many others
Structure and Bonding
Ceramic materials are inorganic compounds consisting of metallic and non-metallic
elements which are held together with ionic and/or covalent bonds.

So this means that the bond between ceramics could be ionic, could be covalent and
could be both ionic and covalent. To elaborate this consider this chart:
 Compound M.P Covalent Ionic

MgO 2800 27% 73%

Al2O3 2050 37% 63%
SiO2 1700 49% 51%
Si3N4 1900 70% 30%
SiC 2500 89% 11%
Calculation of Ionic Character
The percentage of ionic character of a ceramic material/compound can be calculated
by:

Percentage of ionic character = {1 � exp[-0.25(XA-XB)2]}x100

Where:

XA = Electro-negativity of A element
XB = Electro-negativity of B element
Example
Calculate ionic and covalent characters of CaF2 and SiC
For CaF2
Using formula:
Percentage of ionic character = {1 � exp[-0.25(XA-XB)2]}x100
= {1 � exp[-0.25(1-4)2]}x100
= {1 � exp[-0.25(3)2]}x100
= {1 � exp[-2.25]}x100
= {1 � 0.105}x100
= 89.5%
So Percentage of covalent character = 10.5%

For SiC
Using formula:
Percentage of ionic character = {1 � exp[-0.25(XA-XB)2]}x100
= {1 � exp[-0.25(2.5-1.8)2]}x100
= {1 � exp[-0.25(0.7)2]}x100
= {1 � exp[-0.1225]}x100
= {1 � 0.88}x100
= 12%
So Percentage of covalent character = 88%
Properties of Ceramics
Of oxide ceramics
Oxidation resistant
Chemically inert
Electrically insulating
Generally low thermal conductivity
Of other compounds ceramics
Low oxidation resistance
Extreme hardness
Chemically inert
High thermal and electrical conductivity
High melting points of ceramics
Ceramic Melting point

Si3N4 1750-1900�C
Al2O3 2050�C
SiC 2300-2500�C
ZrO2 2500-2600�C
WC 2775�C
ThO2 3300�C
HfO2 3890�C
High hardness of ceramics
Ceramic Vicker hardness

Al2O3 3360 Kpsi

SiC 4680 Kpsi
ZrO2 (+ CaO) 1980 Kpsi
NaCl 30 Kpsi
Fused SiO2 780 Kpsi
Diamond 13,780 Kpsi
Most ceramics are usually crystalline
Grain boundary structure
Typical grain size of ZrO2

Processing of Ceramics
Raw materials selection criteria
Powder sizing
Pre-consolidation
Shape forming processes
Pressing
Casting
Plastic forming
Other forming processes
Sintering
Final machining
Quality control
Non-destructive testing

Raw material selection criteria

Purity
Effect of any impurity depends upon chemistry of both matrix material and the
impurity, distribution of impurity and service conditions. Example of Ca in Si3N4.
It effects high temperature properties of the ceramic material.
Particle size and reactivity
Consolidation/shaping depends upon particle size and its distribution.
Explanation.
Reactivity of ceramic powder play an important role during sintering (of the
compacted shape).
Polymorphic form
Polymorphic transformations can play an important role in the sintering
operations. Example of Si3N4 and SiC
Powder Sizing
Screening
Air classification
Elutriation
Ball milling
Attrition milling
Vibratory milling
Fluid energy milling
Hammer milling
Precipitation
Freeze drying
Laser
Plasma
Calcining
Pre-consolidation
These are special treatments done before compacting/consolidation

Three types of consolidations are there and pre-consolidation of each is

different. These are:
Pressing
Slip casting
Injection moulding

A comparison of three is shown

Pressing
Binder addition
Lubricant addition
Sintering aid addition
Slip casting
Slurry preparation
Binder addition
pH control
Viscosity control
De-airing
Injection moulding
Thermoplastic addition
Plasticizer addition
Wetting agent addition
Lubricant addition
De-airing

Functions of additives to ceramics

Binder
Green strength
Lubricant
Mold release, inter-particle sliding
Plasticizer
Improving flexibility of binder film, allowing plastic deformation of granules
Deflocculant
pH control, particle-surface charge control, dispersion
Wetting agent
Reduction of surface tension
Functions of additives to ceramics (cont.)
Water retention agent
Retain water during pressure application
Fungicide and bactericide
Stabilize against degradation with aging
Sintering aid
Aid in densification
Antistatic agent
Charge control
Antifoam agent
Prevent foam
Foam stabilizer
Strengthen desired foam
Example of additives used
Organic Inorganic

PVA Mg-Al silicates

Waxes Soluble silicates
Cellulose Colloidal silica
Thermoplastic & thermosetting resins Colloidal alumina
Lignins Clays
Rubbers Bentonites
Proteins Aluminates
Bitumens Phosphates
Chlorinated hydrocarbons Borophosphates
Gelatins
Shape forming processes
Pressing
Uniaxial pressing
Isostatic pressing
Hot pressing
Hot isostatic pressing

Casting
Slip casting
Thixotropic casting
Soluble mold casting
Shape forming processes (Cont)
Plastic forming
Extrusion
Injection moulding
Transfer moulding
Compression moulding

Others
Tape forming
Flame spray
Green machining
Processes for shaping crystalline ceramics: (a) pressing, (b) isostatic pressing,
(c) extrusion, (d) jiggering, and (e) slip casting.#
Sintering
The densification of a particulate ceramic compact is technically referred to as
sintering
Sintering is essentially a removal of the pores between the starting particles,
combined with growth together and strong bonding between adjacent particles
The following criteria must be met before sintering can occur:
A mechanism for material transport must be present
A source of energy to activate and sustain this material transport must be present
Sintering Mechanism
Sintering can occur by a variety of mechanisms. The main mechanisms are:

Vapour phase sintering

Material transport mechanism is evaporation-condensation and the driving energy is
difference in the vapour pressure
Solid state sintering
Material transport mechanism is diffusion and the driving force is difference in
free energy/chemical potential
Liquid state sintering
Material transport mechanism is viscous flow, diffusion and the driving force is
capillary pressure, surface tension
Sintering furnace
During firing, clay and other fluxing materials react with coarser particles to
produce a glassy bond and reduce porosity
Effect of sintering temperature on density
Effect of sintering time on density
Joining Ceramics
Final Machining
Difficuilt to machine due to their high hardness and brittle nature

The tool must have higher hardness than the ceramic being machined

Ceramic material can be machined by following mechanisms

Mechanical machining
Chemical machining
Thermal machining

Mechanical Machining
Mounted abrasion machining
Small, hard, abrasive particles bonded to or immersed in a softer matrix
These abrasive particles can be SiC, Al2O3, Al2O3-ZrO2, or other hard ceramics and
matrix could be rubber, organic resin, glass etc
For hard ceramic materials diamond is the most efficient abrasive, mounted in a
matrix of soft metal/organic resin
Free abrasion machining
In it we use loose abrasive material along with coolant like water, oil etc
Used for final polishing
Impact abrasion machining
Al2O3 and SiO2 are used frequently
They are fired/blasted by high velocity gases
Abrasion depends upon particle size, material nature and angle

Chemical Machining
Photo-etching
Some glass compositions can be chemically machined into very complex geometries
using this photo-etching technique
Electrical discharge machining
It is done only on electrical conductive materials
Its advantage is no mechanical load and disadvantage is limited to conducting
ceramic materials only
Laser machining
Very few work is done on laser machining of ceramic materials
The mechanism of material removal appeared to be localized thermal shock spalling

Quality control
Quality control is required throughout processing of any material/product, and
ceramics are no exception.

The degree of QC is determined by the criticality of the application.

Critical/demanding applications may require destructive sampling, proof testing,

or non-destructive inspection (NDI).

Glass
A state of matter as well as a type of ceramic
As a state of matter, the term refers to an amorphous (noncrystalline) structure
of a solid material
The glassy state occurs in a material when insufficient time is allowed during
cooling from the molten state for the crystalline structure to form
As a type of ceramic, glass is an inorganic, nonmetallic compound (or mixture of
compounds) that cools to a rigid condition without crystallizing

Why So Much SiO2 in Glass?

Because SiO2 is the best glass former
Silica is the main component in glass products, usually comprising 50% to 75% of
total chemistry
It naturally transforms into a glassy state upon cooling from the liquid, whereas
most ceramics crystallize upon solidification

Other Ingredients in Glass

Sodium oxide (Na2O), calcium oxide (CaO), aluminum oxide (Al2O3), magnesium oxide
(MgO), potassium oxide (K2O), lead oxide (PbO), and boron oxide (B2O3)

Functions:
Act as flux (promoting fusion) during heating
Increase fluidity in molten glass for processing
Improve chemical resistance against attack by acids, basic substances, or water
Add color to the glass
Alter index of refraction for optical applications
Glass Products
Window glass
Containers � cups, jars, bottles
Light bulbs
Laboratory glassware � flasks, beakers, glass tubing
Glass fibers � insulation, fiber optics
Optical glasses - lenses

Glass-Ceramics
A ceramic material produced by conversion of glass into a polycrystalline
structure through heat treatment

Proportion of crystalline phase range = 90% to 98%, remainder being unconverted

vitreous material
Grain size - usually between 0.1 - 1.0 ?m (4 and 40 ?-in), significantly smaller
than the grain size of conventional ceramics
This fine crystal structure makes glass-ceramics much stronger than the glasses
from which they are derived
Also, due to their crystal structure, glass-ceramics are opaque (usually grey or
white) rather than clear

Processing of Glass Ceramics

Heating and forming operations used in glassworking create product shape
Product is cooled and then reheated to cause a dense network of crystal nuclei to
form throughout
High density of nucleation sites inhibits grain growth, leading to fine grain size
Nucleation results from small amounts of nucleating agents in the glass
composition, such as TiO2, P2O5, and ZrO2
Once nucleation is started, heat treatment is continued at a higher temperature to
cause growth of crystalline phases

Advantages of Glass-Ceramics
Efficiency of processing in the glassy state
Close dimensional control over final product shape
Good mechanical and physical properties
High strength (stronger than glass)
Absence of porosity; low thermal expansion
High resistance to thermal shock
Applications:
Cooking ware
Heat exchangers
Missile radomes
Applications
Barium Titanate (often mixed with strontium titanate) displays Ferro-electricity,
meaning that its mechanical, electrical, and thermal responses are coupled to one
another and also history-dependent. It is widely used in electromechanical
transducers, ceramic capacitors, and data storage elements.
Bi-Strontium calcium copper oxide, a high temperature superconductor
Boron carbide, which is used in some personal, helicopter and tank armor.
Boron nitride is structurally iso-electronic to carbon and takes on similar
physical forms: a graphite-like one used as a lubricant, and a diamond-like one
used as an abrasive.
Applications (Cont)
Bricks (mostly aluminium silicates), used for construction.
Earthenware , which is often made from clay, quartz and feldspar.
Ferrite, which is ferrimagnetic and is used in the core of electrical transformers
and magnetic core memory.
Lead zirconate titanate is another ferroelectric material.
Magnisium diboride, is an unconventional superconductor
Silicon carbide, which is used as a susceptor in microwave furnaces, a commonly
used abrasive, and as a refractory material.
Applications (Cont)
Silicon nitride, is used as an abrasive powder.
Steatite is used as an electrical insulator.
Uranium oxide, used as fuel in nuclear reactors.
Yttrium barium copper oxide (YBa2Cu3O7), another high temperature superconductor.
Zinc oxide, which is a semiconductor, and used in the construction of varistors.
Zirconium dioxide (zirconia), is used in fuel cells. In another variant,
metastable structures can impart transformation toughening for mechanical
applications; most ceramic knife blades are made of this material.
Modern Trends
In the early 1980s, Toyota researched production of an adiabatic ceramic engine
which can run at a temperature of over 6000 �F (3300 �C). Ceramic engines do not
require a cooling system and hence allow a major weight reduction and therefore
greater fuel efficiency. Fuel efficiency of the engine is also higher at high
temperature, due to Carnot�s theorem. In a conventional metallic engine, much of
the energy released from the fuel must be dissipated as waste heat in order to
prevent a meltdown of the metallic parts.
Modern Trends (Cont)
Work is being done in developing ceramic parts for gas turbine blades. Currently,
even blades made of advanced metal alloys used in the engine�s hot section require
cooling and careful limiting of operating temperatures. Turbine engines made with
ceramics could operate more efficiently, giving aircraft greater range and payload
for a set amount of fuel.

Ceramics are used in the manufacture of knives. The blade of the ceramic knife
will stay sharp for much longer than that of a steel knife, although it is more
brittle and can be snapped by dropping it on a hard surface.
Modern Trends (Cont)
Since the late 1990s, highly specialized ceramics, usually based on boron carbide,
formed into plates and lined with Spectra, have been used in ballistic armored
vests to repel large-caliber rifle fire. Such plates are known commonly as small-
arms protective inserts (SAPI). Very similar technology is used to protect
cockpits of some military airplanes, because of the low weight of the material.
Modern Trends (Cont)
Recently, there have been advances in ceramics which include bio-ceramics, such as
dental implants and synthetic bones. Hydroxyapatite, Ca10(PO4)6(OH)2 (Ca/P = 1.67)
the natural mineral component of bone, has been made synthetically from a number
of biological and chemical sources and can be formed into ceramic materials.
Orthopedic implants made from these materials bond readily to bone and other
tissues in the body without rejection or inflammatory reactions. Most
hydroxyapatite ceramics are very porous and lack mechanical strength and are used
to coat metal orthopedic devices to aid in forming a bond to bone or as bone
fillers. Work is being done to make strong-fully dense nano crystalline
hydroxapatite ceramic materials for orthopedic weight bearing devices, replacing
foreign metal and plastic orthopedic materials with a synthetic natural bone
mineral.
Modern Trends (Cont)
The space shuttle makes use of ~25,000 reusable, lightweight, highly porous
ceramic tiles that protect the aluminum frame from the heat generated during re-
entry into the Earth�s atmosphere.

Turbo Charger
Candidate Materials for Turbocharger
CONCLUSION
In the past few decades Ceramics materials have over powered many metallic and
polymeric materials due to their superior and wide range of properties.
With times to come they will gain more and more importance and the coming time
will bring a revolutionary era in this fascinating material.

Example of Ca

Ca severely decreases the creep resistance of Si3N4 hot-pressed with MgO as a

densification (sintering) aid, but appears to have little effect on Si3N4 hot
pressed with Y2O3 as the densification aid. In the former case, the Ca is
concentrated at the grain boundaries and depresses the softening temperature of
the grain boundary glass phase. In the later case, the Ca is apparently absorbed
into solid solution by the crystalline structure and does not significantly
reduces the refractoriness of the system.
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Particle size effect

A single particle size does not produce good packing. Optimum packing for
particles all the same size results in over 30% void spaces. Adding particles of a
size equivalent to the largest voids reduces the void contents to 26%. Adding a
third, still smaller particle size can reduce the pore volume to 23%. Therefore,
to achieve maximum particle packing, a range of particle size is required.

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Example of Si3N4 & SiC

Alpha Si3N4 is superior to beta Si3N4 as the starting powder for hot pressing. A
similar case is present in SiC. The stable form at high temperature is hexagonal
alpha SiC, so it can be pressed to a greater range as compared to beta SiC which
is cubic and is stable at relatively lower temperature.

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Ceramic - Composite Armor
Ceramic armor systems are used to protect military personnel and equipment.
Advantage: low density of the material can lead to weight efficient armor systems.

Typical ceramic materials used in armor systems include alumina, boron carbide,
silicon carbide, and titanium diboride.
The ceramic material is discontinuous and is sandwiched between a more ductile
outer and inner skin.
The outer skin must be hard enough to shatter the projectile.
Most of the impact energy is absorbed by the fracturing of the ceramic and any
remaining kinetic energy is absorbed by the inner skin, that also serves to
contain the fragments of the ceramic and the projectile preventing severe impact
with the personnel/equipment being protected. (as shown in diagram)

Ceramic - Composite Armor

Cementless fixation: Hydroxyapatite (HA)
Ceramic in medical (Bio-ceramics)

All the material presented in this presentation is included in the course.

Thank you