Ceramics

Objectives:

• Synthesis, Processing, and Applications of ceramic

materials
• Processing and Applications of inorganic glasses
and glass-ceramics

Ref Chapter: Ceramic Materials (in Askeland)

“a non metallic inorganic solid”

W.D. Kingery (1926-2000)
(father of modern ceramics, MIT) 1
 From the Greek word Keramikos: “Fired clay”

Indicating that the desired properties are normally

achieved through high-temperature heat treatment (firing)

Polycrystalline, inorganic, non-metallic

materials that acquire their mechanical
strength through a firing or sintering process

2
History:
Chinese pottery appears during 18,000 BC

Pottery from Mesopotamia, A Ming Dynasty porcelain

vase dated to 1403–1424
5000 BC

3
16th century ceramic tilework, Jerusalem 4
Ceramics in everyday life:

5
Ceramics in life science

Implants
Tissue engineering scaffolds

Ceramics are used in a wide range of technologies such as refractories, spark

plugs, dielectrics in capacitors, sensors, abrasives, etc.
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Ceramics in space science

Brakes Engine

Nose cones

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.
Insulating tiles 7
 (1) Kaolinite:
Al2Si2O5(OH)4

(2) Example of modern

ceramics: Al2O3

8
1

Kaolin: Al2Si2O5(OH)4
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2 Alumina (Al2O3)

Sapphire
Ruby

Corundum
115 million tonnes, over 90% of which is used
in the manufacture of aluminium metal.
10
 There are various classification systems of
ceramic materials, which may be attributed to
one of two principal categories:
Functional classification
or
Chemical composition (oxides, nitrides,
carbides, etc.)

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 Ceramics Metal Polymer
Some comparison: Density Low High Lowest
Hardness Highest Low Lowest
Ductility Low High High
Corrosion High Low Low
resistance
Electrical Average High Low
conductivity
Thermal Low High Low
conductivity

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Processing of ceramics

1. Synthesis
Making ceramic powder is defined as
synthesis of ceramics which is ready for
shaping by crushing, grinding, blending
with different powders, etc.

2. Green ceramics* (green body)

Properly processed powders into
desired shape (shape forming)
* ‘green’ as ‘native’ or ‘fresh’ similar to the term
‘green tomatoes’. "green" because it is ‘raw’

3. Sintering High temperature processing

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1. Synthesis

2. Green ceramics

3. Sintering
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1. Synthesis
Making ceramic powder
Raw material selection criteria
• Depends on the properties required for the finished
product/component
• Purity, particle size, reactivity are the important criteria
Purity: influence strength and oxidation resistance
Example: Calcium decreases the creep resistance of the Si3N4 when hot pressed
with MgO as sintering aid. But it have little effect on Si3N4 when hot-pressed with
Y2O3 as sintering aid. In the first case Ca is concentrated at grain boundaries and
depresses the softening temperature of the grain boundary glass phase. In the
second case, the Ca is apparently absorbed into solid solution by the crystalline
structure and doesn’t significantly reduce the refractoriness of the system.

The impurity have effect on mechanical, electrical and

optical properties. Example: doping
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 Particle size
• Depending on the objective of the component; particle packing, shrinkage
and porosity will be effected by particle size
• A single particle size distribution do not produce good packing
• Optimum packing of single particle size result in 30% porosity
• Addition of particle size of largest voids (to the above case) reduces the
porosity to 26%
• Real ceramic particles are irregular in shape and do not fit into ideal
packing
• Hence, porosity after compaction is generally 35% and can go above 50%
• Low porosity and fine grain size are good for high strength (however, there
are applications where strength is not the primary criterion)
Reactivity
• The primary driving force towards densification during sintering is the
difference in surface free energy
• Very small particle with high surface area have high surface free energy and
have a strong thermodynamic drive to decrease their surface area by
bonding together
Particle size distribution and reactivity are important in determining the sintering temperature
and time. (eg: finer size can achieve densification in lower temperature and time) 16
As mentioned earlier, control over particle size distribution is required to achieve
optimum properties for the intended applications

E.g.: high strength ceramics requires very fine particles of size 1 m

Techniques for powder preparation

Mechanical Chemical Miscellaneous

Screening Precipitation Calcining
Ball milling Sol-gel Combustion
Hammer milling plasma
Roll crushing Hydrothermal
Freeze drying

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Making ceramic powder using crushers

The powder is poured into screen of

required mesh size.
e.g. mesh 16 represent 16 sieves per
square inch

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Ball milling
The common method for reducing particle size is
ball milling. A ball mill is a barrel (usually made
of a ceramic) that rotates on its axis and is
partially filled with a grinding medium (called
media) in the form of spheres, cylinders, or rods.

The media should have a high density as this Cross section of a ball mill showing
provides for the most effective collisions. The the movement of the media as the
choice of media is also based on cost, wear mill rotates about its axis. This
resistance, and the possibility of introducing method produce 0.5–10 μm size
contamination into the powder. particles

Commonly used media: WC, ZrO2, Steel, Al2O3, SiO2

Contamination is a problem in ball milling. During milling the media and mill wall is
wearing. Milling of Al2O3 powder with SiO2 media result 0.1% contamination/hour

Milling produces broad particle size distribution rather than

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narrow particle size that achieved in screening
Two types: (d) Dry milling
(a) Wet milling (lubricants:
ethylene glycol, Advantages:
Advantages: oleic acid, • Avoids drying of the powder
• Low power required glycerine) • Avoids reaction of the powder
• No dust • Less media and lining wear
• Higher rotational speed
• Good homogenisation
• Smaller particle size than dry method
• Compatible with spray drying 20
Sol-gel method
The sol-gel process consists of two steps
• First we form a sol
• Then we transform this into a gel

The method is used for the fabrication of metal oxides, especially

the oxides (SiO2, TiO2, etc). The process involves conversion of
monomers (metal alkoxides, e.g. titanium isopropoxide) into a
colloidal solution (sol) that acts as the precursor for an integrated
network (gel) of network polymers.

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 Hydrolysis &
condensation Gelation
Solution of metal Sol (solution)
alkoxides

Drying Firing Dense

Polymeric gel Dried gel product

Steps involved in sol-gel process

• Form a stable dispersion (sol) of particles less than 0.1 m in diameter
in a liquid
• By change in concentration (evaporation of a portion of the liquid),
aging or addition of a suitable electrolyte, induce polymer like, three-
dimensional bonding to occur throughout the sol to form a gel
• Evaporate the remaining liquid from the gel
• Increase the temperature to convert the dehydrated gel to the ceramic
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composition
Various steps in sol-gel method for SiO2 particles

SiO2

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The rigidity of the gel prevents migration or segregation of atoms during
drying and assures homogeneity at the molecular level. The resulting
powder has high surface area and small particle size (20 -50 nm). Due to
fine particle size and high surface area and homogeneous distribution of
atoms the sol-gel derived powders can be sintered at lower temperature
than powder prepared by conventional mechanical processes.

A number of metal alkoxides are commercially available in high purity

form. To make metal oxide powders from these precursors we start with a
solution (a “sol”) of the metal alkoxide in alcohol.
Two reactions then occur: Hydrolysis and condensation. The condensation
product can be hydrolyzed further to form a crosslinked, three-
dimensional network, lead to gel.

Gelation times vary from seconds to several days. The dried gel is calcined
completely convert it to oxide. Powders produced by the sol-gel method
are amorphous. A crystallization step is required to produce crystalline
bodies, which is often performed after sintering.
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 Calcining

Calcining refers to a high temperature treatment of powders to modify

the characteristics of the powder. By calcining; coarsening,
decomposition, reaction and dehydration have been possible.

Coarsening involves crystallite growth or fusing small particles together

to produce large particles.
Decomposition involves converting composition of carbonates/nitrates
to oxides.

Dehydration is important in preparation of cement and plaster. The

partially dehydrated gypsum is known as plaster.
CaSO4.2H2O (gypsum)  CaSO4. 1/2H2O (plaster)

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2. Green ceramics (green body)

Many shaping methods are used for ceramic products and

these can be grouped into three basic categories:

1. Powder compaction: dry pressing, hot pressing, cold

isostatic pressing, …
2. Casting: using a mold containing, a liquid or slurry: slip
casting, tape casting, …
3. Plastic forming: extrusion, injection molding, etc.—using
pressure to shape the green ceramic

Slurry is a suspension of ceramic particles in a liquid

The green body is strong enough to be handled and machined

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Some common additives are added to the ceramic powder during the
preparation of green body formation. Examples are binders and plasticisers

• Binder is a component that is added to hold the powder together while

we shape the body. Increase the green body strength and provide
lubrication. The binder provides the green body with strength sufficient
to survive the handling process between shaping and sintering. One of
the most important requirements for the binder is that we must be
able to eliminate it from the compact during the firing process without
any disruptive effect. Eg: water, polyvinyl alcohol,…

• Plasticizer is the component of a binder that keeps it soft or pliable; it

improves the rheological properties. Improves the flexibility.
Eg: polyethylene glycol, dibutyl phthalate

The distinction between binder and plasticizer is sometimes not too clear

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The following (common) techniques are
involved in forming ceramic powders into a
desired shape (green body):

• Uniaxial (Die) Pressing

• Isostatic Pressing
• Injection Molding
• Extrusion
• Slip Casting
• Gel Casting
• Tape Casting
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• Uniaxial (Die) Pressing
Die pressing is the powder
compaction method involving
uniaxial pressure applied to the
powder placed in a die between
two rigid punches.
Uniaxial (die) pressing is
effectively used for mass
production of simple parts

Die pressing, which is conducted at the room

temperature is called cold pressing
If the pressing process is conducted at
increased temperature it is called hot pressing
limited to simple solid shapes, such as flat
plates, blocks, and cylinders.
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The scheme of the die pressing method
(i) (ii) (iii)

Uniaxial pressing involves the compaction of powder into a rigid die by

applying pressure along single axial direction through a rigid piston
(mechanical or hydraulic).
Dry pressing: powder containing moisture below 4%
Wet pressing: feed powder containing 10-15% moisture content

Pros: fast production, easy automation

Cons: improper density (density variation), die wear, cracking
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• Isostatic Pressing

The ceramic powder with other

(CIP) components are weighed into the
rubber mold. The sealed bag is placed
inside a high-pressure chamber that is
filled with a fluid (oil/ water) and is
hydrostatically pressed. The pressures
can vary from 20 MPa to 1 Gpa. Once
pressing is complete, the pressure is
released slowly, the mold is removed
from the pressure chamber, and the
fluid pressed component is removed from
the mold.

Isostatic pressing is the powder compaction method involving

applying pressure from multiple directions through a liquid or
gaseous medium surrounding the compacted part. 31
The advantages:
• Wide range of shapes and sizes can be
produced
• Uniform density of the pressed product
• Low tooling costs
The disadvantages:
• Poor dimensional control for complex
shapes
• Products often require green machining
• Long cycle times (between 5 and 60
minutes) give low production rates
• Difficulty in automation

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 Hot isostatic pressing (HIP) involves isostatic
pressing conducted at increased temperature. As a
pressure medium a gas (Nitrogen or Argon) is used.
Temp 2000 C, pressure = 200 Mpa (20000 psi)

This process is referred as HIPing

HIP combines pressing and sintering, causing consolidation of powder particles,

healing voids and pores. The part shrinks and densifies, forming sound high
strength structure.

Pros: produces dense materials without growing the grains

Cons: cost

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• Injection Molding

(shape)

Nozzle
Injection molding is the method of compaction of ceramic powder fed and
injected into a mold cavity by means of a screw rotating in cylinder.
• Mixing the ceramic powder with 30% - 40% of a binder (low melt polymers)
• Injection of the warm powder with molten binder into the mold by means of the screw
• After injection, removal of the part from the mold after cooling down of the mixture
during this time the thermoplastic polymer hardens
• Removal of binder is achieved by heating above the volatilisation temperature of the
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polymer
Injection molding method is widely used for manufacturing small
parts having complex shapes

Because of the large volume fraction of organic material used in

the mixture, there is a high degree of shrinkage of injection-
molded components during sintering. Shrinkage of 15–20% is
typical, so precise control of component dimensions is difficult.

The major limitation is that the initial tooling costs of the mold can
be quite high (but re-usable)
Incomplete mold filling and solidification defects (during
drying) are the common defects in injection modelling

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Extrusion
Extrusion involves forcing a
deformable mass through a Ceramic
Ceramic mix mold
die orifice (like toothpaste mix
from a tube).

The ceramic powder mixed with

binder, plasticizer and lubricant is
passed through the die
(A) (B)
Extrusion of (A) a rod and (B) a tube

The process is widely used to produce ceramic components having a

uniform cross section and a large length-to-diameter ratio such as
ceramic tubes and rods 36
Common defects in extrusion

Warpage or distortion: can occur during drying or firing due to

density variations
Laminations: are cracks that generally form a pattern
Tearing: surface cracks that form as the materials exits the extruder

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 • Slip Casting
Think of a ceramic art show piece. How might have it made?
The slip is poured into a mold (usually plaster of Paris: 2CaSO4·H2O) that has
been made by casting round a model of the required shape. The water passes, via
capillary action, into the porous plaster leaving a layer of the solid on the wall of the
mold (see next slide). Once a sufficient thickness has been cast, the surplus slip is
poured out and the mold and cast are allowed to dry.

Slip casting is used for

manufacturing fine china,
teapots, jugs, sinks, sanitary
ware, thermal insulation parts.

Ceramic product made by slip

casting is hollow 38
Various steps in slip casting

Then it will be sintered 39

 • Gel Casting
Gel Casting is a process of shape forming
slurry prepared from ceramic powder mixed
with a solution of organic monomer. When
the slurry is poured into a mold, the
monomer polymerizes, forming a gel that
binds ceramic powder particles into a strong
complex-shaped part. The parts may be
machined before firing.

The process is economical and used for manufacturing

large complex shapes parts such as turbine rotors.

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The basic principle of gel casting process is that ceramic powders
are combined with a solvent, usually water, a dispersant, and
organic monomers to form a high-solids-content, fluid slurry. The
slurry is poured under conditions into a casting mold where by an
initiator and catalyst the organic monomers polymerize to form a
3-D polymer network of a solid gel in the shape of the mold. The
gelcast part goes through a volatiles removal step by calcination.
The part is then sintered using the conventional firing treatment
for the particular ceramic material.

The main advantage of gel casting is the

forming of complex ceramic shapes.

Example: gel casting of alumina powder is achieved by the in situ polymerisation

of acrylamide monomer (C2H3CONH2) in the presence of ammonium persulfate
(NH4)2S2O8) initiator and tetramethylethylendiamine as catalyst.
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• Tape Casting
Tape casting is used for preparing thin ceramic sheets or films.

Containing ceramic powder,

binder, plasticizer

Rotation

Tape Casting is used for manufacturing multilayer

ceramics for capacitors and dielectric insulators. 42
 Tape Casting

Ceramic sheet

The person is drying the casted sheet by hot air

Till now we have discussed shaping of the ceramic powder using various methods. After this
step a densification step called as sintering is required to get enough strength for the
component. See it from next slide onwards. 43
 3. Sintering
Sintering (Firing) of ceramic
Sintering is defined as: The thermal treatment of a powder
or green compact at a temperature below the melting point
of the main constituent, for the purpose of increasing its
strength by bonding together of the particles. This
densification of particulate ceramic compact is referred to
as sintering

Sintering temperatures are in

the range of 500 – 1500 0C.
Time: 1 h to several hours
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 We have defined the term ‘Sintering’ in the previous slide.
The densification of a particulate ceramic compact is technically
referred to as sintering. Sintering essentially removes the pores
between the starting particles (accompanied by shrinkage of the
component), combined with growth together and strong
bonding between adjacent particles. The following criteria must
be met for sintering

1. A mechanism of material transport must be present. The

primary mechanism for transport are diffusion and viscous
flow.
2. A source of energy to activate and sustain this material
transport must be present. Heat is the primary source of
energy, in conjunction with energy gradient due to particle-
particle contact and surface tension.

(The sintering is known for centuries, scientific understanding of

‘sintering’ have been achieved during last 60- years) 45
Sintering (the thermal treatment) has various stages, which is termed as
(i) initial stage, (ii) intermediate stage and (iii) final stage

I II III

Details of process occurring in each stages are given in upcoming slides

46
 (i) initial stage
Changes occur during this stage:

• Rearrangement
• Neck formation

Initial particle Rearrangement Neck formation

47
(ii) intermediate stage
Changes occur during this stage:

• Neck growth
• Grain growth
• High shrinkage

Neck growth Lengthening of grain Neck growth and grain

48
Volume shrinkage boundaries boundary growth continue
(ii) intermediate stage (cont…)

Neck between particles grows. Porosity decreases and the center of the
original particles move closed together. This result in shrinkage
equivalent to the amount of porosity decrease. The grain boundaries
begin to move so that one particle (grain) begins to grow while the
adjacent grain is consumed. Intermediate sintering continues as long as
pore channels are interconnected and ends when pore become isolated.
Most of the shrinkage during sintering occurs during second stage.

49
 (iii) final stage
Changes occur during this stage:

• Much grain growth

• Discontinuous pore phase
• Grain growth with porosity
elimination

Grain growth with Grain growth with Grain growth with

discontinues pore phase porosity reduction porosity elimination
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 (iii) final stage (cont…)

Final stage involves the final removal of porosity. The porosity is removed
by vacancy diffusion along grain boundaries. Therefore, the pores must
remain close to the grain boundaries. Pore removal and vacancy diffusion
are aided by movement of grain boundaries and controlled grain growth. If
the grain growth is too rapid, the grain boundaries can move faster than
the pores and leave them isolated inside a grain. Elimination of this pores
are difficult. Therefore, grain growth must be controlled to achieve
maximum removal of porosity.

Grain growth is driven by surface energy. Curved grain

boundaries move in such a way that then gain a larger
radius of curvature (i.e. straighten out).

51
SEM microscopy image showing the changes
occurring during different stages of sintering
is shown below powder

52
Density variation during sintering. The density increase is highest in
intermediate stage.

53
Mechanisms of sintering

1: Grain boundary diffusion

The operating mechanism of 2,5: bulk diffusion
sintering to happen are: 4: evaporation and condensation
3: surface diffusion
54
Mechanisms of Sintering
(another scheme)

neck
pore

SEM image showing the neck

formation during sintering
55
 SEM image of

Sintered at 1500 0C for 3 h

56
Generally, sintering at higher temperature produce higher grain size. This slide and next
57
slide provide some examples
Grain growth
58
 Advantages of Sintering

Particular advantages :
1. the possibility of very high purity for the
materials and their great uniformity
2. absence of segregated particles and inclusions
(as often occurs in melt processes)
3. no requirement for deformation to produce
directional elongation of grains

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Learning objectives

1. Classification of ceramics
2. General properties of ceramics
3. Important steps in ceramics processing
4. Characteristics of ceramic powder and its effects
5. Techniques for powder preparation
6. Role of binder and plasticiser in green body formation
7. Various techniques for green body formation, its pros and cons
8. Sintering: various stages and mechanism

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