Dry pressing (die compaction) for MSE 302 Lab

FORMING OF CERAMICS
The overall process consists of three steps:
• filling of the die
• powder compaction
• ejection of the compacted powder.

For relatively simple shapes

(e.g., disks) with a height-to-
diameter ratio of 0.5–1.0.

http://www.substech.com

upper punch

mould body (die) The double action mode is capable

powder
of providing better packing
lower punch homogeneity and is commonly
used in industry.
single-action double-action
compaction mode compaction mode
Feed Material: Powders and Granules
Fine powders do not flow very well and are difficult to compact homogeneously
 Granulation (intentional agglomeration to increase flowability)

Figure 6.22 shows a commercial spray-

dried Al2O3 powder
Compaction Defects

Fig 6.31 Illustrations of typical defects in die compaction of dry or semidry powders:
(a) delamination, (b) end capping, (c) ring capping, and (d) vertical cracks.

Use lubricants to reduce friction

Benefits of lubricants Internal lubricant: a material positioned

• Reduce die wall-particle friction inside the granule to reduce interparticle
 less pressure for green friction
body ejection
• Yield more uniform pressed parts External lubricant: a material positioned on
 uniform density distribution the outside of the granule (or powder) to
• Significantly increases tool (die) life reduce friction at the die wall
 cost
• Reduce sticking and time required for
cleaning
 increased mass production
rate
 Ceramic Fabrication Processes
An Introductory Overview

1.1 INTRODUCTION
The subject of ceramics covers a wide range of materials can be divide it
into two parts:

• Traditional ceramics: developed since the earliest civilizations. They

are pottery, structural clay products, and clay-based refractories, with
which we may also group cements, concretes and glasses.

• Advanced (also known as technical, special, fine, and engineering)

ceramics: for electrical, magnetic, electronic, and optical applications
(sometimes referred to as functional ceramics) and for structural
applications at ambient as well as at elevated temperatures (structural
ceramics).
Chemically, with the exception of carbon, ceramics are nonmetallic, inorganic
compounds.
Oxide materials:
Silicates: koalinite (Al2Si2O5(OH)4), mullite (Al6Si2O13)
Simple oxides: alumina (Al2O3), Zirconia (ZrO2)
Complex oxides: Barium titante (BaTiO3), superconductors (YBa2Cu3O6+s,0≤s≤1)
Nonoxide materials:
Carbides: silicon carbide (SiC), boron carbide (BC)
Nitrides: silicon nitride (Si3N4),boron nitride (BN)
Borides: titanium diboride (TiB2)
Silicides: molybdenum disilicide (MoSi2)
Halides: lithium fluoride (LiF)

Structurally, all materials are either crystalline or amorphous (also referred

to as glassy). Crystalline ceramics (and metals) are actually polycrystalline—
they are made up of a large number of small crystals, or grains, separated from
one another by grain boundaries.
In ceramics as well as in metals, we are concerned with two types of
structure, both of which have a profound effect on properties:

• Structure is at the atomic scale: the type of bonding and the structure (crystalline
or amorphous). The intrinsic properties are determined by the structure at the atomic
scale and are properties that are not susceptible to significant change by modification
of the microstructure, properties such as the melting point, elastic modulus, coefficient
of thermal expansion, and whether the material is brittle, magnetic, ferroelectric, or
semiconducting.

• Structure is at a larger scale: the microstructure, which refers to the nature,

quantity, and distribution of the structural elements or phases in the ceramic (e.g.,
crystals, glass, and porosity). Many of the properties critical to the engineering
applications of materials are strongly dependent on the microstructure (e.g.,
mechanical strength, dielectric constant, and electrical conductivity).
Intrinsically, ceramics usually have high melting points and are therefore
generally described as refractory.

They are also usually hard, brittle, and chemically inert. This chemical inertness
is usually taken for granted, for example, in ceramic and glass tableware and in
the bricks, mortar, and glass of our houses. However, when used at high
temperatures, as in the chemical and metallurgical industries, this chemical
inertness is severely tried.

The applications of ceramics are many. Usually, for a given application one
property may be of particular importance, but in fact, all relevant properties
need to be considered. We are therefore usually interested in combinations of
properties. See the application details given in Lecture 0.
 Chemical Composition

Ceramic
fabrication Intrinsic

Figure 1.1
Microstructure Properties

The important relationships between chemical composition, atomic structure,

fabrication, microstructure, and properties of polycrystalline ceramics are
illustrated in Fig. 1.1.

The intrinsic properties must be considered at the time of materials selection.

For example, the phenomenon of ferroelectricity originates in the perovskite crystal
structure, of which BaTiO3 is a good example. For the production of a ferroelectric
material, we may therefore wish to select BaTiO3.
BaTiO3 perovskite crystal structure

Displacement of Ti+4 in the octahedral position with

respect to oxygen atoms gives rise to dipole moment
formation  required for ferroelectricity. The role of
the fabrication process, then, is to produce
microstructures with the desired engineering
properties. For example, the measured dielectric
constant of the fabricated BaTiO3 will depend
Ti 4+ Ba 2+ O 2-
significantly on the microstructure (grain size,
porosity, and presence of any secondary phases).

Normally, the overall fabrication method can be divided into a few or several
discrete steps, depending on the complexity of the method
 called processing steps
1.2 CERAMIC FABRICATION PROCESSES

The main fabrication methods are divided into three groups,

depending on whether the starting materials involve a gaseous phase,
a liquid phase, or a solid phase

(solid)

C
A: Gas-Phase Reactions

• Reaction between gaseous species

 e.g., vapor deposition

• Reaction between a liquid and a gas

 e.g., directed metal oxidation

• Reaction between a gas and a solid

 e.g., reaction bonding (or reaction forming)
A-1: Chemical Vapor Deposition (CVD): a process by which reactive molecules
in the gas phase are transported to a surface at which they chemically react and
form a solid film.

• A well-established technique to deposit all classes of materials, including metals,

ceramics, and semiconductors  for a variety of applications.
• Large areas can be coated  mass production.
• Thick films or monolithic bodies can also be produced  deposition to desired thickness.
• The general objective for any design is to provide uniform exposure of the
substrate to the reactant gases.

• Process variables for CVD  flow rate of the reactant gases, the nature and
flow rate of any carrier gases, the pressure in the reaction vessel (~1–15
kPa), and the substrate temperature (films are produced preferably by
endothermic reactions)

http://www.azonano.com/article.aspx?ArticleID=3432
Example: For fiber-reinforced ceramics by chemical vapor infiltration (CVI).

Reactant gases
Desired temperature
Side view

Forced flow of the reacting gas into

the preform using pressure and
temperature gradients

Fibers preformed into Material deposited in the

shape and dimensions Top view interstices between the fibers

http://en.wikipedia.org/wiki/Chemi
cal_vapor_infiltration

SiC matrix composites reinforced with SiC or C fibers

SiC + 45 vol% fiber (+ open porosity=%10)  fracture toughness of 30 MPa.m1/2 up to 1400°C

Unreinforced SiC  3 MPa.m1/2

Advantages:
• Fairly low fabrication temperatures for ceramics and composites with high melting
points that are difficult to fabricate by other methods or require very high fabrication
temperatures.
• The low reaction temperatures also increase the range of materials that can be coated
by CVD, especially for the highly refractory coatings.
Disadvantages:
• Very slow deposition rate of 1 -100 μm/hours  production of monolithic bodies can
therefore be very time consuming and expensive.
• Development of a microstructure consisting of fairly large, columnar grains which
leads to fairly low intergranular strength.

Large, columnar grains fairly low

intergranular strength

Substrate

CVD methods primarily to the formation of thin films and coatings

A-2: Directed metal oxidation: (Dimox or Lanxide process): for the production
of porous and dense materials as well as composites.

Gas + Liquid → solid

3/2 O2 (g) + 2Al (l) → Al2O3 (s) (oxidation of Al metal to form Al2O3 ceramic)

O2 gas
Al (l) Al2O3 (s)
(columnar grains) Si, Ge, Sn, or Pb), the oxide coating is no
crucible
The material produced in this
way consists of two phases: the
oxidation product (e.g., Al2O3),
which is continuous and
interconnected, and unreacted
metal (Al alloy).
Al2O3 (s) layer at the top forms a protective
layer and prevents further reaction of O2 and Al.
If the temperature is in the range of 900–
1350C and the aluminum alloy contains a few
percent of Mg and a group IVA element (e.g.,
longer protective. Instead, it contains small
pores through which molten metal is drawn up
to the top surface of the film, thereby
continuing the oxidation process.
Oxide growth rate is a few centimeters per
day.
For the production of composites, a filler material (e.g., particles, platelets, or
fibers) is shaped into a preform of the size and shape desired of the product.

SiC fiber + Al2O3/Al matrix.

Figure 1.6
The method has been used to produce composites with not only matrices of
oxides but also nitrides, borides, carbides, and titanates.

Composite systems produced by the method include matrices of

Al2O3/Al, AlN/Al, ZrN/Zr, TiN/Ti, and Zr and fillers of Al2O3, SiC,
BaTiO3, AlN, B4C, TiB2, ZrN, ZrB2, and TiN.

Advantages:
• Growth of the matrix into the preform involves little or no change in
dimensions. The problems associated with shrinkage during densification
in other fabrication routes (e.g., powder processing) are therefore avoided.
• Large components can be produced readily with good control of the
component dimensions.
 A-3: Reaction Bonding: a porous solid preform reacts with a gas (or a liquid)
to produce the desired chemical compound and bonding between the grains.
Reaction bonding is used on a large scale as one of the fabrication routes
for Si3N4 and SiC ceramics.

Example: Si3N4 production:

Si → Shaping → Pre-heating → Machining to → reaction → Si3N4

powder (dry pressing, in Ar required bonding (reaction
Slip casting, atmosphere shape and (in N2 gas bonded or
injection molding) T= 1200°C dimensions T=1200-1400°C) RBSN)

• The Si3N4 consists of 60–90 wt% of the  phase and the remainder being –Si3N4.
Example: Reaction bonded Al2O3 (RBAO) => Al2O3, Al, O2 + additives (e.g., SiC,
ZrO2) => for composite applications

During heat treatment in an oxidizing atmosphere (commonly air), the Al oxidizes to

nanometer-sized - Al2O3 crystals below 900C which undergo a phase transformation to
–Al2O3 up to 1100C.

FIGURE 1.7 Scanning electron micrograph showing the microstructure of a reaction

bonded aluminum oxide (RBAO) sample. The white phase is ZrO 2 (20 vol%) and the
dark phase is Al2O3
Advantages:
• Little or no shrinkage (very close dimensional tolerances for the
finished components)
• Little or no grain growth
• Low cost

Disadvantages:
• Unreacted metalic phase (e.g., Si powder)  detrimental to high
temperature properties (deterioration of the mechanical strength at
temperatures above1200C)
• The RBSN has a porosity of 15–20%
B. Liquid precursor methods

A solution of metal compounds  solid

Examples:
• Sol-gel method  production of simple and complex oxides
• Polymer pyrolysis method  non-oxides (e.g. Si3N4, SiC)

B-1: SOL-GEL: a solution of metal compounds or a suspension of very

fine particles in a liquid (referred to as a sol) is converted into a highly viscous
mass (the gel).

Sol Gel

http://www.rsc.org/chemistryworld/2012/10/injectable-hydrogels-medicinal-use
Procedures
• Prepare a solution of metal alkoxides in an appropriate alcohol.
M(OR)x where M is metal (e.g., Si, Al, B etc) and R is an alkyl group (e.g., CnH2n+1).
• Add water to this solution either in the pure state or diluted with more alcohol.
• Stirring at temperatures normally 50–90C and with suitable concentration of reactants
and pH of the solution, hydrolysis and condensation reactions may occur, leading to
the formation of polymer chains.

Taking the example of a tetravalent metal (e.g., M=Si), the reactions:

hydrolysis reaction  M(OR)4 + H2O → M(OR)3OH + ROH

condensation reaction  M(OR)3OH + M(OR)4 → (RO)3-M-O-M-(OR)2 + ROH
(Polymer chain with metal ions )

• Polymerization interlinking and cross-linking of the polymer chains  a marked increase in

the viscosity of the reaction mixture and the production of a gel.
• The gel has a continuous solid network and a finite shear modulus.
• The solids content of the gel can be quite low due to excess water and alcohol used (i.e., <5–10
vol% in many cases). The remainder of the volume consists of liquid that must be removed
prior to firing.
Advantages:
• Materials with high purity can be produced
• Materials with exceptionally good chemical homogeneity (mixing at the
molecular level)
• Lower densification (or sintering) temperature

Disadvantages:
• The starting materials (e.g., the metal alkoxides) can be fairly expensive
• Cracking, warping, and considerable shrinkage (e.g., 90 vol% during drying
and 50 vol% during firing) are common problems during drying.

Mainly because of these problems in drying, the sol–gel route has

seen little use for the fabrication of monolithic ceramics. Instead it
has seen considerable use for the fabrication of small or thin articles,
such as films, fibers, and powders.
 B-2: POLYMER PYROLYSIS:

• Polymer pyrolysis refers to the pyrolytic decomposition of metal-

organic polymeric compounds to produce ceramics.

• The chain backbone in polymers contains elements other than carbon

(e.g., Si, B, and N ) or in addition to carbon.

• While potentially a large field, the polymer pyrolysis route has been
applied most effectively to the production of nonoxide ceramic fibers,
in particular, fibers of two silicon-based ceramics, SiC and Si3N4, and
to a more limited extent BN and B4C.
Advantages:
• ease of processing into the desired shape
• relatively low conversion temperature to nonoxide ceramics.

Disadvantages:
• A large volume change up to 75 vol% in SiC and Si3N4. As outlined for the sol–gel
process, such large volume changes make the fabrication of monolithic ceramics very
difficult.
• Used as binders in the processing of nonoxide ceramic powders, but they are very
expensive and lead to a significant increase in the fabrication costs.

The polymer pyrolysis route finds its most important use

in the production of thin objects, in particular fibers and,
to a more limited extent, coatings.
C. Fabrication from powders
Starting materials  solid (powders)
heat
Powders → Ceramics

Two methods;
i. Melt casting –melting followed by casting or forming into shape
ii. Firing of compacted powders

C-1: Melt casting

- For ceramics that crystallize relatively easily  solidification of the melt is
accompanied by rapid nucleation and growth of crystals (i.e., grains).
Uncontrolled grain growth is generally a severe problem  undesirable
properties such as low strength.

- For technical ceramics  either high melting point (e.g., 2600°C for ZrO2)
or low decomposition temperature (e.g., Si3N4). Therefore, this method is not a
suitable method for the preparation of technical ceramics.

The melt casting method is therefore limited to the

fabrication of glasses.
An important variation of glass processing is the glass ceramic route

Powder mixture
heat

Melt
Shaping and Cooling

Glass
Two stage heat treatment:
a lower temperature hold to induce nucleation of crystals
followed by one or more higher temperature holds to
promote growth of the crystals throughout the glass.

Glass ceramics

Glass ceramics are by definition 50% crystalline by volume and

most are > 90% crystalline (Glass noncrystalline or amorphous)
 The potential range of glass ceramic compositions is fairly broad because the
method depends only on the ability to form a glass and to control its
crystallization.

The highest volume applications are cookware and tableware, architectural cladding,
stove tops, and stove windows.
Almost all glass ceramics developed so far are based on silicate glass
compositions:

1. Simple silicates, e.g., compositions based on the Li2O–SiO2

system
2. Fluorosilicates
3. Aluminosilicates, e.g., compositions based on Li2O–Al2O3–SiO2
(LAS) and MgO–Al2O3–SiO2 (MAS) systems water

Generally, glass ceramics have higher strength, chemical

durability, and electrical resistance and can be made
with very low thermal expansion coefficients, giving 700°C
excellent thermal shock resistance. flame

http://people.sabanciuniv.edu/~m-gulgun/index.html/CAYBARDAGI.htm
C-2: Firing of compacted powders

Although in principle this route can be used for the production of both glasses
and polycrystalline ceramics, in practice it is hardly ever used for glasses because
of the availability of more economical fabrication methods (e.g., melt casting).

Powder

Mixing (with binder and additives)

Consolidation (e.g., die pressing, slip casting, injection

molding, extrusion, tape casting)

Porous shaped powder form

Close attention be paid to each processing
(green body or powder compact)
step in the fabrication route if very specific
properties are to be achieved.
Firing (or heating)

Dense polycrystalline product

Because of its importance and widespread use, the fabrication of polycrystalline

ceramics from powders will form the main focus of this course.
1.3. PRODUCTION OF POLYCRYSTALLINE
CERAMICS FROM POWDERS: An overview

A. Powder Synthesis and Powder Characterization:

In most cases, the fabrication process starts from a mass of powder obtained
from commercial sources. But, need to know
• knowledge of powder synthesis methods.
• the physical, chemical, and surface characteristics of the powder.

Powder characteristics  size

size distribution
shape
degree of agglomeration
chemical composition
purity

Powder synthesis methods  mechanical (grinding or milling)

 chemical (chemical reactions under carefully
controlled conditions such as precipitation, sol-gel,
hydrotermal method, etc)
Some of the chemical methods, while often more expensive than the
mechanical methods, offer unprecedented control of the powder characteristics.

FIGURE 1.16 An example of a submicrometer

TiO2 powder prepared by controlled chemical
precipitation from a solution

Hydrothermal method: Uniformly agglomerated

BaTiO3 powders (∼150 nm) consisting of ∼20 nm
primary particles.
Troublesome issues => minor variations in the chemical composition
purity
• causes profound effect on the microstructure and properties of the materials.
• must pay attention to powder quality in powder synthesis steps.

A continuing trend is towards the

preparation of fine powders
(nowadays, towards nanosized
powders).

In principle, the enhanced activity of

fine powders is beneficial for the
attainment of high density bodies at
lower firing temperatures.
A major problem in handling and subsequent consolidation
 agglomeration of powders, particularly when the particle size
decreases below 1 m.

 The packing of the consolidated

powder can be quite nonuniform.
 Little benefit is achieved during the
firing stage.

The use of fine powders therefore

requires proper control of the
handling and consolidation
procedures in order to minimize the
deleterious effects due to the presence
of agglomerates.
 Characterization of the surface chemistry of the powders
TEM : Transmission electron microscopy
SIMS: Secondary ion mass spectroscopy
AES : Auger electron microscopy
XPS : X-ray photoelectron spectroscopy
The spectroscopic techniques have the capability for detecting constituents (atoms,
ions, or molecules) down to the parts per million (ppm) range.

B. Powder Consolidation

Consolidation of ceramic powders or forming  Green body

1) Dry or semidry pressing of the powder in a die
2) Plastic forming methods: mixing of the powder with water or organic
polymers to produce a plastic mass that is shaped by pressing or
deformation (e.g., injection molding and extrusion)
3) Colloidal methods: casting from a concentrated stable suspension or
slurry (e.g., slip casting and tape casting).
Powder-based production of advanced ceramics

Organic
Powder Powder Drying Sintering
Forming binder
synthesis dispersion
T<100C removal T = ½-¾ of Tmelting
T<600-800C
- Solid state - Polymers - Dry pressing
- Precipitation - Dispersants - Slip casting
- Sol-gel - Plastilizers - Tape casting
- Hydrothermal - Mold release - Injection molding
- Defoaming - Extrusion
(Pechini,
agents
molten salt, (Gel casting,
etc.) etc.)
Powder-based production of advanced ceramics

Problems in processing:
Density gradient in green body:
• agglomeration of powders in synthesis and dispersion steps,
• density gradients in forming step

After sintering, the fabricated body will usually have a heterogeneous

microstructure that limits the engineering properties and reliability.

Solution:
Utilize colloidal techniques for the consolidation of powders from a suspension:
• Stabilize or disperse powders in a liquid (normally water) to prevent
agglomeration.
The suspension is then made to settle by itself, by filtration, or by centrifuging.
Colloidal cast versus dry pressing Fig 1.17 Uniformly packed submicrometer
of ZrO2 powders TiO2 powder produced by consolidation from a
stable colloidal suspension.
C. The Firing Process
Heat
Green body Dense product
(firing or sintering)
Tsintering = ½-¾ of Tmelting

Example: pure, single phase material (Al2O3)

Sintering temperature of Al2O3 is commonly 1400-1650°C (Tmelting=2073°C).

The powder does not melt; instead, the joining together of the particles and the
reduction in the porosity (i.e., densification) of the body occurs by atomic
diffusion in the solid state  solid state sintering.

The driving force for sintering is the reduction in surface free energy of the
consolidated mass of particles. This reduction in energy can be accomplished by
atom diffusion processes that lead to either densification of the body or coarsening
of the microstructure.

Coarsening: The progressive enlargement of the grain size or pore size during
sintering (due to diffusion, coalescence or solution- repreciptation processes).
Key parameters in sintering
• temperature,
• particle (or grain) size,
• applied pressure,
• sintering atmosphere

The rates of densification and coarsening are enhanced by higher sintering

temperature and by fine particle size. Densification is further enhanced by the
application of an external pressure.

Microstructural inhomogeneities present in the green body (e.g., density, grain

size, and compositional variations)  seriously hinder the ability to achieve high
density and to adequately control the fabricated microstructure.

Solution  enhanced powder quality and powder consolidation by colloidal

methods.
If densification is not successful in solid-state sintering due to coarsening (e.g., in
covalently-bonded ceramics such as Si3N4 and SiC), the solutions are:

Liquid phase sintering  use of an additive that forms a small amount of liquid-phase
between the grains at the sintering temperature. Amount of liquid phase is < 10 vol% (or
as low as possible)
Examples: BaTiO3+1%TiO2, Si3N4+5%MgO, Al2O3+5% talc, ZrO2+CaO/SiO2
(<1%), MgO + 1-3% LiF

External pressure  hot pressing and hot isostatic pressing

The applied pressure has the effect of increasing the driving force for densification
without significantly affecting the rate of coarsening. However, a common drawback of
pressure sintering is the increase in the fabrication costs.
Examples: Si3N4, SiC

Viscous sintering  viscous glass or liquid present at the sintering temperature flows
under the action of the capillary forces of the pores to fill up the porosity of the body.
Amount of liquid phase is > 40 vol%.
Examples: Glass, clay-based ceramics such as porcelain
D. Ceramic Microstructures
Microstructure  Processing method
For solid-state sintering in which all the porosity is successfully removed,
a microstructure consisting of crystalline grains separated from one another
by grain boundaries is obtained.

FIGURE 1.21 Incomplete removal of the porosity during

Figure 1.19a. Al2O3 ceramics solid-state sintering of CeO2 results in a microstructure
consisting of grains, grain boundaries, and pores.
Depending on the nature and amount of liquid, the grain boundary phase
may be continuous, thereby separating each grain from the neighboring grains
or may be discontinuous, e.g., at the corners of the grains

Fig 1.20 Microstructure produced by High resolution TEM micrograph of Si3N4

liquid-phase sintering, under an applied
pressure, of Si3N4 with MgO additive. A
continuous glassy phase, 0.8 nm thick,
separates the crystalline grains.
showing a triple-point and intergranular film
of oxynitride glass (the thickness of the
parallel bars is ~ 1 nm)
http://www.ualberta.ca/~hanifi/Ceramics%20a
nd%20Glasses.htm
Traditional clay-based ceramics sintered by viscous sintering

Fig 1.22 A commercial sanitary ware body produced by firing a mixture of clay,
feldspar and quartz, showing a fairly complex microstructure containing some residual
feldspar (F), porosity (P), and quartz (Q).
Ceramic Composites  for high temperature structural applications.

Example: SiC fibers + Al2O3 matrix  high mechanical tougness

 Control the starting powder quality:  particle size distribution
 shape
 composition
 impurities

a major influence on
the development of
the microstructure

Impurities can lead to the

presence of a small amount of
liquid phase at the sintering
temperature, which causes
Fig 1.23 Large grained region of microstructural heterogeneity
resulting from an impurity in hot pressed Al2O3. selected growth of large
individual grains (Fig 1.23).

Impossible to achieve a fine

uniform grain size.
In general, any nonuniformity in the green body is exaggerated in the
sintering process, leading to the development of cracklike voids or large
pores between relatively dense regions

Fig 1.24 Cracklike void produced by a ZrO2

agglomerate shrinking away from the
surrounding Al2O3/ZrO2 matrix during firing.
White regions: ZrO2
Black regions: Al2O3
Unless high porosity is a deliberate requirement, we normally wish to achieve:
 high density
 small grain size
 uniform microstructure

Insufficient control of the sintering conditions such as;

• sintering temperature,
• time at sintering temperature,
• rate of heating,
• sintering atmosphere
can lead to defects and the augmentation of coarsening  impossible to attain
desired microstructure.

The sintering of many materials (e.g., Si3N4, lead-based ferroelectric ceramics,

and -alumina) require control of the atmosphere in order to prevent
decomposition or volatilization.
Possibility of chemical reactions between the phases:

Al2O3 + SiC fiber composite  Al2O3 can be made mechanically tougher (i.e.,
less brittle) by the incorporation of SiC fibers.

However, oxidation of the SiC fibers leads to the formation of an SiO2 layer on
the fiber surfaces. The SiO2 can then react with the Al2O3 to form
aluminosilicates with a consequent deterioration of the fibers.

Prolonged exposure of the system to oxygen will eventually lead to the

disappearance of the fibers. A primary aim therefore would be the control of the
atmosphere during densification in order to prevent oxidation.
Two solid phases  general requirement is a uniform distribution of one phase
in a uniformly packed matrix of the other phase.
Close attention must be paid to the processing steps prior to firing (e.g., during the
mixing and consolidation stages) if this requirement is to be achieved in the
fabricated body.

FIGURE 1.25 The nonuniform

distribution of fine ZrO2 particles
(light phase) in Al2O3 (dark phase) is
seen to result in a region of
uncontrolled grain growth during
firing.

ZrO2 controls grain growth of Al2O3

Defects produced in the processing steps prior to firing cannot normally be reduced or
eliminated. In most cases, these defects are enhanced during the firing stage.

In general, properties are controlled by the microstructure (e.g., density and grain size),
but the defects in the fabricated body have a profound effect on those properties that
depend on failure of the material (e.g., mechanical strength, dielectric strength, and
thermal shock resistance).

Failure events are almost

always initiated at regions of
physical or chemical
heterogeneity.

Fig 1.26 Crack nucleation at a

large grained heterogeneity
during deformation of a hot-
pressed Al2O3 body
A case study in processing: The fabrication of TiO2 from powders

Careful control of the powder quality and the powder consolidation method
1) Conventional route:
TiO2 powder (commercial)

Dry mix with additives, e.g., Nb2O5 and BaCO3  Additives aids sintering

Calcine (900°C for 10-20 h)

Ball mill with binder (16 h)  Binder aids the powder compaction process
 Ball milling breaks down agglomerates

Spray dry  to form spherical agglomerates

Die pressing

Shaped powder form

Firing or sintering (1400°C for 10 h)

Dense polycrystalline product

2) Colloidal method:
Titanium Isopropoxide (I)
 Controlled hydrolysis of Ti
or
tetraisopropoxide or Ti tetraethoxide
Titanium Ethoxide (II)

Dissolve in appropriate alcohol;

mix with water/alcohol solution

Precipitation of nearly spherical and

“monodisperse” titania powder

Wash powder to purify;

Disperse in basic aqueous solution to produce a stable dispersion; FIGURE 1.16 An example of a
Consolidate by gravitational or centrifugal settling; submicrometer TiO2 powder prepared by
Dry in vacuum controlled chemical precipitation from a
solution

Shaped powder form

Firing or sintering (800-1050°C for 1.5 h)

Dense polycrystalline product

Process parameter Conventional method Colloidal method

Powder particle size (m) 1 0.1 (I)

0.4 (II)
Sintering temperature (°C) 1400 800 (I)
1050 (II)
Sintering time (h) 10 1.5
Final relative density (%) 93 >99
Final grain size (m) 50-100 0.15 (I)
1.2 (II)

Reduction in sintering time and temperature

No milling, no binder, no additive→ Highly pure
Higher density with much smaller grain size
BUT higher cost and not suitable for mass production

Substantial benefits can be achieved in sintering and

microstructure control when the powder quality is carefully
controlled and the powder packing is homogenous.