You are on page 1of 81

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:

a. Traditional Ceramics
b. 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

H CaF 2: Large He
2.1 -

Li Be C F Ne
1.0 1.5 SiC: Small 2.5 4.0 -

Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -

K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -

Rb Sr I Xe
0.8 1.0 2.5 -

Cs Ba At Rn
0.7 0.9 2.2 -

Fr Ra
0.7 0.9 Table of Electronegativities
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 1750-1900ºC
Al2O3 2050ºC
SiC 2300-2500ºC
ZrO2 2500-2600ºC
WC 2775ºC
ThO2 3300ºC
HfO2 3890ºC
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

ZrO2 NaCl
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.

©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.
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

©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.
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).
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.
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 µ m (4 and 40 µ -
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

Ceramic Rotor
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.

The last shocking words


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.
BACK
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.

BACK
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.

BACK
BACK
BACK
BACK
BACK
BACK
BACK
BACK
BACK
BACK
Schematic of a tape casting machine. (Source: From
Principles of Ceramics Processing, Second Edition, by
J.S. Reed, p. 532, Fig. 26-6. Copyright © 1995 John
Wiley & Sons, Inc. Reprinted by permission.)

BACK
BACK
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
Ceramic-
Outer hard Discontinuous
skin

Projectile

Personnel
and
Equipment

Inner
ductile
skin

Ceramic Armor System


BACK
Cementless fixation: Hydroxyapatite
(HA)

Zimmer HA coated
Plasma Spray HA coating on Dental APR® Hip Stem
Implants (Sun et al., 2001)
BACK
Ceramic in medical (Bio-ceramics)

Zimmer PureForm
Ceramic Crowns Ceramic Copings Zinc Phosphate
Dental Cements

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

Thank you