KIG3010: Engineering Materials

Processing Ceramics

Henk Metselaar

Universiti Malaya

October 2024
 Processing steps

• In general, processing follows all or some of the following

steps:
• Acquisition and treatment of raw materials.
• Powder preparation.
• Calcination.
• Forming.
• Drying.
• Sintering.
• Finishing.
• Quality control.
Various processing methods and intended applications.
 Processing of Refractory Ceramics

• These are processed as shaped bricks or as unshaped (cast)

material.
• Due to the large size of bricks, sintering shrinkage must be
minimised.
• This is achieved by a high packing, thanks to a wide Particle
Size Distribution (PSD).
• Packing fraction of about 85 % is achieved as smaller particles
enter interstices between larger particles (recall that dense
packing of equal-sized spheres is about 74 %).
• Heat treatment usually melts a small fraction of clay-based
material, gluing the particles together.
• The mixture can be dispersed in a liquid (water) and cast in
place and dried (much like concrete) then fired in place.
 Melt Processing
• Glass (both sheet glass and container glass) make up the
largest volume of this.
• Raw materials (sand, lime, soda) are fed into a lined tank.
• As the materials passes through the tank it is first heated to
1600 °C to react and form a homogeneous bubble-free melt,
then cooled to forming temperature (1050 °C–1200 °C).
• Liquid is also formed in Viscous Glass Sintering (VGS) as in
glazes and enamels and (20 %–60 %) in Viscous Composite
Sintering (VCS) as in whiteware and porcelain.
• The amorphous phase formed after decomposing kaolin reacts
with alkali-rich material to form a liquid. Some reactions:
>500 °C 950 °C
Al2Si2O5(OH)4 Al2Si2O7 + H2O
amorphisation glass

1125 °C
Al2O3 + SiO2 + Al6Si2O13 Al6Si2O13 + SiO2
cristobalite
Simplified ternary solid–liquid–pore diagram illustrating importance of
liquid formation in various ceramic densification processes.
SEM image of the etched microstructure of a porcelain triaxial porcelain
showing quartz filler (Q), needle-like mullite (MII ) formed on reaction of
clay, and flux and finer, more equiaxed mullite (MI ) from decomposition
of clay. Solution rims are seen around the quartz grains as they dissolve
in the alkali-rich liquid.
Time–temperature plot of the various stages in glass ceramic processing.
TN is the temperature giving maximum nucleation, while TG gives
maximum crystal growth. The dashed line indicates that after shape
forming, the component can be cooled to room temperature and then
reheated to crystallize.
 Low Temperature Processing

• Ceramic bonds react with water to form hydrates phases that

act as glue between ceramic particles.
• This is used widely as cement in construction.
• The bonds are calcium silicates or aluminium calcium silicates.
• Alternatives are phosphates and geopolymers
(aluminosilicates, usually from natural sources or waste
materials).
 Other Processes

• Coatings (CVD, PVD)

• Infiltration (esp. for composites containing fibres).
• Metal-gas reaction (for coatings, e.g. Al2O3 on Al).
• Porous ceramics.
• Advanced and emerging processes (nanomaterials and additive
manufacturing).
 Raw Materials

• Natural raw materials:

• Clay (containing kaolinite (Al2Si2O5(OH)4), halloysite
(Al2Si2O5(OH)4), pyrophyllite (Al2(Si2O5)2(OH)2),
montmorillonite (Al1.67(Na,Mg)0.33(Si2O5)2(OH)2) etc.)
• Flux materials: feldspar (KAlSi3O8, NaAlSi3O8, CaAl2Si2O8),
nepheline syenite (Na2Al2Si2O8).
• Others: talc (Mg3(Si2O5)2(OH)2, asbestos (Mg3Si2O5(OH)4,
wollastonite (CaSiO3), sillimanite (Al2SiO5).
• Industrial raw materials: minerals that are mined and
minimally processed.
• Synthetic raw materials: raw materials that have undergone
chemical processing.
 Aluminium Oxide

• Produced from bauxite in the Bayer process.

• Used in porcelain, alumina laboratory ware, metal-casting
moulds, high-temperature cements, wear-resistant parts,
sandblast nozzles, armour, medical components, abrasives,
refractories, and a variety of other components.
 Magnesium Oxide

• Mostly obtained from calcining MgCO3 or from seawater.

• Used in high-temperature applications.
 Silicon Carbide

• Synthesised from quartz and carbon in the Acheson process:

2200 °C
SiO2 + 3 C SiC + 3 CO

• SiC is used for high-temperature kiln furniture, electrical

resistance heating elements, grinding wheels and abrasives,
wear resistance applications, incinerator linings, varistors,
light-emitting diodes, and also gemstones cut from single
crystals.
 Silicon Nitride

• Si3N4 can be produced from the reaction of silicon with

nitrogen:

1250 °C–1400 °C
3 Si + 2 N2 Si3N4

• Higher purity is obtained from silica:

3 SiO2 + 6 C + 2 N2 Si3N4 + 6 CO

or from silicon tetrachloride:

3 SiCl4 + 4 NH3 Si3N4 + 12 HCl

 Raw Material Selection

• Purity (amount and type of impurities)

• Particle size, particle size distribution and reactivity
(sinterability).
Effects of porosity in the powder compact on the porosity and grain size
of Al2O3 after densification.
 Powder Preparation and Sizing

Techniques for Powder Preparation and Sizing

Mechanical Chemical Miscellaneous

Screening Precipitation Calcining
Elutriation Sol-gel Fluidized bed
Air classification Liquid mix Rotary kiln
Ball milling Decomposition Combustion synth.
Attrition milling Freeze drying
Vibratory milling Hot kerosene drying
Turbomilling Plasma
Fluid energy milling Laser
Hammer milling Hydrothermal
Roll crushing
Schematic cross section showing the key elements of a typical ball mill.
Effects of the use of a milling aid on (a) the pressed density and (b) fired
density of a low-soda calcined Al2O3.
Particle size distribution of silicon powder as a function of milling time.
Schematic of an attrition mill.
Comparison of the particle size reduction of a ferrite powder by vibratory
milling and ball milling.
Turbomilling of barium ferrite powder compared to other milling
techniques. Particles 0.1 µm in diameter were produced in 2 h with
turbomilling.
 Sol-gel synthesis

Preparing a powder using sol-gel involves the following steps:

1. Form a stable dispersion (sol) of particles with a diameter of
less than 0.1 µm in a liquid.
2. By change in concentration, ageing or addition of a suitable
electrolyte, induce polymer-like, 3-D bonding to occur
throughout the sol to form a gel.
3. Evaporate the remaining liquid from the gel.
4. Increase the temperature to convert the dehydrated gel to the
ceramic composition.
 Sol-gel synthesis

Example:
Silica-based compositions have been prepared usig tetraethyl
orthosilicate (TEOS) or colloidal SiO2. TEOS is soluble in ethanol.
Colloidal SiO2 is soluble in water and contains a cation stabiliser
such as Na+ or NH4+. The water-based procedure is easiest. The
colloidal SiO2 plus nitrates of the required metal cations is mixed
into a homogeneous sol. The pH is controlled with nitric acid
(HNO3), Depending on the system and the pH, a gel will form in
several minutes to a day.
 Liquid Mix Process
The Pechini or amorphous citrate process has the following steps:
1. An aqueous solution is prepared with metal alkoxides,
hydrated oxides or carbonates in an 𝛼-hydroxycarboxylic acid
such as citric acid; the ratio of ions can be precisely
controlled. The acid complexes with the metal ions to form
polybasic acid chelates.
2. A polyhydroxy alcohol such as ethylene glycol is added, and
the liquid is heated to 150 °C–250 °C to allow the chelates to
undergo polyesterification.
3. Heating is continued to remove excess water, resulting in a
polymeric “resin”.
4. The temperature is increased to about 400 °C to char or
decompose the resin.
5. The temperature is further increased to 500 °C–900 °C to form
crystallites of the mixed oxide composition. The crystallites
are typically 20 nm–50 nm and clustered into agglomerates.
Transmission electron microscope image of ultrafine La0.76Sr0.24CrO3
powder prepared by the glycine–nitrate process, a variant of liquid mix.
Schematic drawing illustrating the hydropyrolysis or spray-roasting
process. An example reaction is 2 FeCl2 + MnCl2 + 3 H2O + 12 O2
MnFe2O4 + 6 HCl
 Hydrothermal Synthesis

Hydrothermal synthesis (or solvothermal synthesis if solvents other

than water are used) comprises nucleation and growth of particles
in a solvent at elevated temperature and pressure. Typically
100 °C–350 °C and <15 MPa. Many ceramics can be prepared with
this simple technique but it is a batch process.
Self-propagating High temperature Synthesis (SHS)

• This starts with a reactive metal powder.

• At high temperature it reacts exothermically with carbon,
boron, hydrogen etc.
• The heat released by the reaction speeds up the reaction.
• Many borides, carbides, carbonitrides, cemented carbides,
chalcogenides, hydrides, intermetallics, nitrides and silicides
can be formed with this technique.
 Function of Additives in Ceramics Processing

Additive Function
Binder Increases green strength and provides
lubrication
Lubricant Mould release, die-wall and interparticle
friction reduction
Compaction aid Aids in particle rearrangement during pressing
Plasticiser Rheological aid, improves flexibility of binders,
allows plastic deformation of granules
Deflocculant Reduce flocculation and aid dispersion by
pH control, control of particle surface charge
Wetting agent Reduces surface tension
Water retention agent Retains water during pressure application
Antistatic agent Charge control
Antifoam agent Prevents foaming and bubble formation
Chelating agent Deactivates undesired ions
Biocides Prevent microbial growth
Sintering aids Aids in densification
Dopants Modify product properties
Phase stabilisers Control of the crystalline phase
 Granulation

• Granulation is necessary to have a free-flowing powder.

• Main methods are spray drying and spray granulation.
• Despite the similar names, these are two different processes.
• Spray granulation involves spraying a binder solution on a dry
powder and mixing until homogeneously sized granules are
formed.
Spray-drying setup.
 Batch Calculations

• Raw materials (e.g. carbonates) are often different from final

materials (e.g. oxides).
• Final compositions are usually given as molecular formulae:
CaSiO3 requires 1 mole of Ca per mole of Si.
• But raw materials are weighed on a scale.
• So some calculations are necessary to obtain the correct
weights.
 Sintering

• Most ceramics processing yields a green product with particles

held more or less strongly together by a binder.
• To convert this into a final product, a heat treatment
(sintering) is needed.
• This will eliminate part/most/all of the porosity in the
product and form strong bonds between the particles.
• This requires:
1. A driving force (usually surface tension),
2. A source of energy (usually heat), and
3. A mechanism for material transport (usually diffusion or
viscous flow).
 Stages of Sintering

• Sintering is commonly thought of as occurring in three stages:

1. The initial stage involves rearrangement of particles and initial

neck formation at the contact point between each particle.
The rearrangement consists of slight movement or rotation of
adjacent particles to increase the number of points of contact.
2. The intermediate stage sees most of the [Link] necks
between particles grow, particle centres move closer together
and porosity is eliminated. Grain boundaries are formed and
larger grains start growing at the expense of smaller grains.
The pore phase remains continuous.
3. In the final stage, closed pores are formed. Grain boundary
pores can be eliminated but pores in the interior of grains or
pores that are too large shrink very slowly. Much grain growth
occurs.
Changes that occur during the initial stage of sintering. (a) Starting
particles, (b) rearrangement, and (c) neck formation.
Changes that occur during the second stage of sintering. (a) Neck
growth and volume shrinkage, (b) lengthening of grain boundaries, and
(c) continued neck growth and grain boundary lengthening, volume
shrinkage, and grain growth.
Changes that occur during the final stage of sintering. (a) Grain growth
with discontinuous pore phase, (b) grain growth with porosity reduction,
(c) grain growth with porosity reduction, and (c) grain growth with
porosity elimination.
 Sintering Mechanisms

Sintering Type Material Transport Mechanism Driving Energy

Vapour-phase Evaporation-condensation Differences in vapour pressure
Solid-state Diffusion Differences in free energy or chemical potential
Liquid-phase Viscous flow, diffusion Capillary pressure, surface tension
Reactive liquid Viscous flow, solution-precipitation Capillary pressure, surface tension
 Vapour Phase Sintering

• In vapour phase sintering the material transport occurs in the

vapour phase. This is not a very common mechanism since for
most ceramics the vapour pressure is too low.
• Material evaporates at places of high surface energy (small
positive radius of curvature) and condenses on places of low
surface energy (large or negative radius of curvature).
(properly speaking this should be called
sublimation-deposition).
• This mechanism leads to neck formation but not to approach
of the particle centres. There is no shrinkage or densification.
Schematic of vapour-phase material transport.
Effect of particle size or surface curvature on the pressure difference and
relative vapour pressure across a curved surface

Material Surface Pressure Relative Vapour

Diameter(µm) Difference (MPa) Pressure (𝑃
𝑃 /𝑃0 )
Water (25 °C) 0.1 2.8 1.02
1.0 0.28 1.002
10.0 0.03 1.0002
Liquid Co (1450 °C) 0.1 67.3 1.02
1.0 6.7 1.002
10.0 0.67 1.0002
Silica glass (1700 °C) 0.1 12.1 1.02
1.0 1.2 1.002
10.0 0.12 1.0002
Solid Al2O3 0.1 36.2 1.02
1.0 3.6 1.002
10.0 0.36 1.0002
 Solid-state Sintering

• Sintering is driven by the surface energy.

• The transport mechanism is diffusion (along grain boundaries
or through the lattice).
• This leads to particle approach and hence densification.
• In case of lattice diffusion, shrinkage can be modelled by:
𝑚
Δ𝐿 𝐾𝛾𝑎3 𝐷∗ 𝑡
=( )
𝐿0 𝑘𝑇 𝑑𝑛

𝛾 surface energy, 𝑎3 volume of diffusing vacancy, 𝐷∗

self-diffusion coefficient, 𝑘𝑇 thermal energy, 𝑑 particle
diameter. Usually 𝑛 ≈ 3 and 𝑚 ≈ 0.3 − 0.5.
Schematic of solid-state material transport.
Typical sintering rate curves showing the effects of temperature and time.
(a) simple data plot of shrinkage versus time during sintering, (b) same
data plotted as a log-log graph of the shrinkage versus time data.
 Solid-state Sintering

• The shape and size (distribution) of the powder is very

important.
• Powder with a broad particle size distribution can be packed
denser.
• Large particles may bridge pores, making them hard to
eliminate.
• Exaggerated grain growth can occur, which can again trap
pores.
• To avoid exaggerated grain growth in Al2O3, add a little MgO
to the powder.
Example of exaggerated grain growth in sintered Al2O3 involving a single
grain
Example of exaggerated grain growth in sintered Al2O3 where all the
grains have grown large and trapped porosity within the grains.
Comparison of the microstructure and translucency of relatively pore-free
Al2O3 (a) with that of opaque Al2O3 containing pores trapped in grains
(b). Translucent Al2O3 tubes are used in sodium vapour lamps (c) that
provide energy efficient street lights.
 Solid-state Sintering

• Solid-state sintering requires high temperatures, making it

expensive.
• Cost is justified when second phases on the grain boundary
would make the ceramic susceptible to corrosion (e.g. by body
fluids in prostheses or Na vapour in lamps).
• Dopants can increase the defect concentration and speed up
diffusion considerably.
 Liquid Phase Sintering

• Silicate systems generally form a liquid phase at the sintering

temperature.
• Factors controlling liquid sintering are:
1. Particle size
2. Viscosity
3. Surface tension
4. Temperature
5. Wetting of particles by the liquid
• Wetting liquid generates capillary pressure (over 7 MPa)
which:
1. Rearranges particles
2. Creates interparticle pressure, promoting material transport
Schematics of types of microstructures that result from liquid-phase
sintering. (a) Sintered glass, (b) crystal-liquid structure, (c) grain
boundary glass, (d) glass at triple junctions, and (e) crystallized grain
boundary.
 Liquid Phase Sintering

• Porcelain is made of about 50 % kaolin (≈45 % Al2O3, bal.

SiO2), 25 % potash feldspar (K source) and 25 % quartz
(SiO2).
• Above 1200 °C some 20 %–50 % of the material is liquid (see
phase diagrams).
• The sintered material is largely vitrified (=has become glassy).
• Si3N4 is an advanced example. Additives and surface SiO2
react to form silicates which can dissolve and precipitate Si3N4
at 1750 °C and higher.
Si3N4 containing Y2O3 plus Al2O3 sintering aids; sintered in nitrogen at
(left) 1600 °C, (middle) 1750 °C and (right) 1850 °C. Scale bar is 1 µm.
 Reactive Liquid Sintering

• Reactive liquid sintering is a variation of LPS where a liquid

phase forms during sintering but reacts to form a crystalline
end product.
• This can lead to products with better high temperature
properties.
• An example is SiC-Al2OC. The Al2O3-Al4C3 system has a
eutectic at 1850 °C that forms the liquid. This can react
further with excess Al4C3 till Al2OC is formed, which can go
into solid solution in SiC.
• Sintering conditions can be reduced from 30 min at 2150 °C to
10 min at 2000 °C.
Phase equilibrium diagram of the system Al2O3–Al4C3 showing the
eutectic between Al2O3 and Al4O4C at about 1830 °C.
 Controlling Conventional Sintering

• Factors that control conventional sintering are:

1. Composition
2. Particle size distribution
3. Temperature
4. Time
5. Atmosphere (chemical reaction and valence state)
6. Furnace design
7. Furnace and heating element materials
8. Settering (how products are placed in the furnace)
Examples of some of the types of furnaces used for sintering of ceramics.
(a) Box furnace, (b) Muffle furnace.
Tunnel kiln
Cold-wall furnace.
Induction furnace.
 Sintering problems
• Warpage. This is caused either by sagging at high
temperature, which can be corrected by better supporting the
product, or by uneven shrinkage due to inhomogeneities in the
green product, which can only be addressed in earlier
processing steps.
• Overfiring. This can cause warpage, reaction with furnace
structures, bloating and excessive grain growth.
• Problems with binder burn-out. If pore channels have become
too narrow or closed pores form before binder burn-out is
complete, the gaseous decomposition products cause pressure
build-up. Residual carbon can cause discolouration.
• Decomposition of carbonates/nitrates/sulphates. As with
binders, gaseous products need to escape.
• Polymorphic transformations, such as m-ZrO2 to t-ZrO2 or
high-low quartz, can be accompanied with significant volume
changes causing internal stress.
 Advanced Sintering Processes

• When a ceramic decomposes instead of densifying, it is

necessary to sinter in a pressurised atmosphere containing the
decomposition product. For example:

Si3N4 3 Si(l) + 2 N2(v)

requiring a pressurised nitrogen atmosphere above 1850 °C.

 Hot Pressing

• Application of pressure and high temperature simultaneously:

1. Reduces densification time.
2. Can reduce densification temperature (to about 0.5𝑇m ),
resulting in less grain growth.
3. Reduces residual porosity.
4. This leads to higher strength.
5. Can reduce the amount of sintering aids needed, improving
high-temperature properties.
6. Can be started with loose powder, obviating the need for
binders and other organics.
• HP is usually done at 7 MPa–35 MPa.
• Graphite is widely used as die material.
Schematic showing the essential elements of a hot press.
Comparison of densities and strengths achieved by hot pressing vs.
sintering

Material Sintering Aid Relative RT MOR 1350 °C MOR

Density (%) (MPa) (MPa)
HP Si3N4 5 % MgO 98 587 173
S Si3N4 5 % MgO ∼90 483 138
HP Si3N4 1 % MgO >99 952 414
S Si3N4 BeSiN2 + SiO2 >99 560 –
S Si3N4 6 % Y2O3 ∼98 587 414
HP Si3N4 13 % >99 897 669
Variations in the strength of hot-pressed Si3N4 as a function of direction.
 Limitations of Hot Pressing

• The major limitation is compression of complex shapes (this is

true in general for pressing as well).
• Thick sections need to compress more than thin sections to
obtain the same density but the punch approaches over the
same distance.
• Due to friction the stress is not distributed evenly inside the
part.
• Different die design can mitigate the problems but not
eliminate them.
Problems associated with complex-shape hot pressing. (a) If we assume a
uniform starting preform or powder stack, the preform will have to shrink
different amounts to achieve a uniform final density and the required
shape. (b) A preform with the correct powder distribution has a different
shape than the die. (c) Loose powder fill requires a powder redistribution
during hot pressing.
Nonrigid tooling approaches for hot pressing. (a) Pseudoisostatic
approach. (b) Multiple preforms simulating a flat-plate approach.
 Hot Isostatic Pressing

• A preformed part is densified in pressurised fluid (usually Ar)

at high temperature.
• Isostatic pressure prevents deformation and naturally allows
complex shapes.
• The surface of the part must be impermeable to the fluid.
This requires either pre-sintering or encapsulation in an
envelop, for example glass.
• High density, high strength materials can be obtained.
 Field Assisted Techniques

• Microwave sintering uses absorption of electromagnetic

radiation by the ceramic as the method of heating.
• Electric Current Assisted Sintering (ECAS, EDS, FS, SPS,
DCRS) uses sparks to heat the ceramic.
• The product can achieve high density in a short time at lower
overall temperature. This allows novel materials that would
not otherwise survive sintering due to decomposition,
reaction, phase change.
Schematic diagram of an SPS furnace with cross section view of die,
punches, and sample.
 Chemical Reaction

• Reaction Bonded Silicon Nitride (RBSN) uses a preform made

from elemental Si powder that is then nitrided at
1200 °C–1400 °C. For final high density overpressure sintering
may still be necessary.
• Reaction-Sintered SiC uses a preform from a mixture of SiC
and C that is infiltrated with molten Si.
• With suitable choice of particle size, there is very little
dimensional change during these processes.
(a, b) Molten Si infiltration of SiC plus C preforms to produce dense,
reaction-sintered SiC.
Typical microstructure of Si–SiC material. The light-coloured phase is
residual Si.