Drying and sintering of Ceramics

Drying of cast or extruded articles:

Ceramic articles produced by casting or plastic forming must be dried prior to
binder burnout and firing. Although drying must be rapid to be economical ,
too fast drying may caused cracks in the article. Hence to design an efficient
drying process, a detailed knowledge is required about the distribution of the
liquid with in the product and also kinetics of the liquid movement.

The moisture content of articles produced by casting or plastic forming

typically in the range of 20 to 35%. As drying proceeds the particles move
close-together causing drying shrinkage until all the particles begin to touch
each other.

During this stage of drying, the volume shrinkage is equals to the volume of
inter-particle water removed. Once this condition is attained it is not possible
for the body to undergo further shrinkage. The moisture content at this stage
MT2171/SUA/2023 1
is known as CRITICAL MOISTURE CONTENT (CMC).
The evaporation rate
and the shrinkage as
a function of the
moisture content
during drying of a
moist granular
material.

Critical moisture content depends on amount of porosity

(amount of packing) which is defined by,
1) Shape, size and size distribution of the powder particles.
2) The extent of defloculation
MT2171/SUA/2023 2
MT2171/SUA/2023 3
 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

The change in the volume of a ceramic body as moisture is removed

during drying. Dimensional changes cease after the interparticle water
is gone. MT2171/SUA/2023 4
The development of warping during drying due to (a) pressure gradient
in the liquid (b) moisture gradient in the body and (c) segregation of
particles.
MT2171/SUA/2023 5
 Causes of cracking and warping,

1) Non uniform moisture distribution of the body

2) Non uniform packing

3) Non uniform drying

4) Segregation and preferred orientation of the particles.

When the warping exceed a certain limit the cracks originates in the body.
Poor mould design, poor die design and bad handling of the green body will
also cause cracking.

MT2171/SUA/2023 6
 Sintering of Ceramics
The starting material to form a ceramic material are powders, which are, by
a variety of techniques , put into shape. The green body is thus a
compacted, still porous body (30 - 60% of theoretical density) of grains,
(idealized as spheres). This green body is subsequently heat treated. The
usual sintering temperature is about 2/3 of the melting temperature.
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 ( accompanied by shrinkage of the
component), combined with growth together and strong bonding between
adjacent particles. The following criteria must be met before sintering can
occur,
1) A mechanism for material transport must be present
2) A source of energy to activate and sustain this material transport must be
present.
The primary mechanisms for transport are diffusion and viscous flow.
Heat is the primary source of energy, in conjunction with energy gradients
due to particle-particle contact and surface tension.
MT2171/SUA/2023 7
Sintering categories

1) Solid State Sintering

Occurs by atomic diffusion in the solid state. No
liquid is present. Finally, once sintering is completed
shape of the grain is hexagonal.
2) Liquid Phase Sintering
Small quantity of liquid is present at sintering
temperature may not be sufficient to fill up the
porosity. Change in shape of grains is required to
achieve full density.
3) Viscous Sintering
Viscous liquid present at the sintering temperature
flows under the action of capillary forces to fill up
the pores of the body. A complex case of viscous
sintering in clay-based materials is referred to as
vitrification. Viscous Sintering
MT2171/SUA/2023 8
MT2171/SUA/2023 9
Sintered SiC with sintering aids – Sintered grain structure BST ceramics
Liquid phase sintering MT2171/SUA/2023
– solid state sintering 10
Driving Force for Sintering
As all other irreversible processes, the driving force for sintering is the
lowering of the free energy of the system.

Energy reduction is the elimination of a fraction of the gas/solid interface.

This acts by the way of the pressure difference across a curved surface.

At equilibrium, the energy resulting from compressing the gas (P∆V) exactly
oppose the energy decrease from reducing the surface area (A).

Sintering Process Variables (that can be controlled)

Temperature, Time, Particle size, Composition (including additives) and
pressure (externally applied)

MT2171/SUA/2023 11
Sintering Mechanisms
Polycrystalline materials sinter by diffusional transport of matter where as
amorphous materials sinter by viscous flow. In polycrystalline materials,
matter transport takes place along definite paths that define the mechanisms
of sintering. The matter is transported from regions of higher chemical
potential (referred to as source) to regions of lower chemical potential
( referred to as sink).

There are at least six different mechanisms of sintering in

polycrystalline materials.
1. Surface diffusion
2. Lattice diffusion ( from the surface)
3. Vapor transport
4. Grain boundary diffusion
5. Lattice diffusion ( from the grain boundary)
6. Plastic flow
MT2171/SUA/2023 12
Six distinct mechanisms that can contribute to the sintering of a
consolidated mass of crystalline particles
MT2171/SUA/2023 13
Densifying mechanisms – mechanisms 4 and 5
Non-densifying mechanisms – mechanisms 1-3

MT2171/SUA/2023 14
MT2171/SUA/2023 15
 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

During firing most traditional ceramics, clay and other

fluxing materials react with coarser particles to produce a
glassy bond and reduce porosity.
MT2171/SUA/2023 16
Sintering Variables (that can be externally controlled)
Particle Size: In all sintering mechanisms, small particles mean faster rate.
But the relative importance of particle size (L) varies from process to process.
E.g. The time required to sinter to a desired level
 Viscous flow  L
 Evaporation / Condensation  L2
 Lattice Diffusion  L3
 Grain boundary diffusion  L4
Temperature : All sintering mechanisms involve movement of atoms from
one place to another, passing through an intermediate high energy state. High
temperatures favour the mechanisms for which the activation energy is high.

Pressure : The application of pressure improves the driving force for

sintering. The non densifying sintering mechanisms are not enhanced by the
applied pressure where as the densifying mechanisms are significantly
enhanced.
MT2171/SUA/2023 17
Sintering Measurement Techniques
There are several techniques available to monitor sintering. Possible
measurements include :

micro structural parameters such as pore size, neck size, pore shape and
grain size.

bulk parameters such as density, electrical conductivity, magnetic

permeability, and dielectric strength.

Mechanical properties such as hardness, strength and elastic modulus.

Other parameters such as compact surface area, shrinkage, transparency

and X-ray absorption.

Despite wide array of measurements, a few selected observations prove most

valuable. These might include a combination of surface area, neck size,
shrinkage, porosity or density.

MT2171/SUA/2023 18
 Firing Cracks

Firing Shrinkage MT2171/SUA/2023 Firing Cracks - Dunting

19
 Advanced Sintering Techniques

Sintering

solid state sintering liquid state sintering pressure assisted sintering

mono- poly- liquid prop. liquid prop. hot hot

phasic phasic <15% >15% pressing isostatic
pressing

without with
reaction reaction

MT2171/SUA/2023 20
Although the objective of firing is to achieve higher densities, a
major problem is that the coarsening reduces the driving force
for densification.

The domination of densifying diffusion processes will favor the

production of a dense body. When coarsening processes dominate,
the production of highly porous body will be favoured.

The effects of key material and processing parameters such as

temperature, particle size, applied pressure and gaseous
pressure on the densification are well understood. The rates of
these processes are enhanced by a higher sintering temperature
and by fine particle size. Densification is further enhanced by
the application of an external pressure.
MT2171/SUA/2023 21
 Microwave Sintering of Ceramics
The use of microwave frequency radiation as an alternative energy source for
materials processing has been examined since the early 1950's. Initially the
work focused on low temperature processes such as drying, however in the
mid-1970's the first attempts were made to utilise microwaves in ceramic
sintering.

Microwave sintering is fundamentally different from conventional

sintering based on thermal conduction or radiation. In microwave
heating, heat is generated by interaction of the microwaves with the
atoms, ions, and molecules of the material.

If properly manipulated microwave heating may lead to a number of benefits

such as reductions in manufacturing costs due to energy savings and shorter
processing times. Considering high uniformity of heating, even the
products with the most complex shapes can be processed, whether the
thick-walled parts, walls of variable thickness, or combined full and
hollow sections. MT2171/SUA/2023 22
Microwaves are electromagnetic waves with a frequency in the range
of 0.3 – 300 GHz or equivalently with a wavelength in the range of
1mm to 1 m. Depending on the electromagnetic properties of the
material , microwaves can be transmitted, absorbed or reflected.

When microwave penetrate the material, the electromagnetic field

induces motion in the free bound charges (e.g. electrons and ions)
and in dipoles. The induced motion is resisted because it causes
a departure from the natural equilibrium from the system. This
resistance due to frictional, elastic, and inertial forces leads to
the dissipation of energy. As a result the electric field associated
with the microwave radiation is attenuated and heating of the material
occurs.

Microwave sintering has been used in the sintering of a variety of

ceramics. However, the most detailed studies so far have been carried
out with Alumina both undoped and MgO doped powders.
MT2171/SUA/2023 23
 Pressure Sintering
Sintering with an applied pressure is commonly referred to as
pressure sintering or pressure assisted sintering. The major
advantage of pressure sintering is the ability to significantly
increase the rate of densification. However the major
disadvantage is the high cost of production.
Various ways can be used to transmit an external pressure to
the powder compact during sintering. However, for the
production of ceramics, there are two commonly used
pressure sintering methods.
1. Hot pressing, where the pressure is applied uniaxially to the
powder in a die
2. Hot isostatic pressing, where the pressure is applied
isostatically by means of a gas

MT2171/SUA/2023 24
Hot Pressing
The powder is placed in a die and heated while pressure is applied.
Depending on the furnace, operating temperatures of up to 25000C
can be used. Typical operating pressure range from 10 to 75 MPa.
Some typical die materials that are used in hot pressing are given
below.
Die Material Max. Temp. C Max. Press. MPa Comments
Mo or Mo Alloys 1100 21 Oxidation unless protecetd
Tungsten 1500 24 Oxidation
Al2O3 1400 207 Expensive, brittle
SiC 1500 276 Expensive, brittle
TaC 1700 55 Expensive, brittle
Graphite (standard) 2500 34.5 Severe oxidation above
1200C

Graphite (special) 2500 138 Severe oxidation above

1200C
MT2171/SUA/2023 25
As in conventional sintering, improvements in powder quality
lead to clear benefits for densification. Powders for hot
pressing should be fine (<1mm), have a narrow size
distribution and contain no hard agglomerates. Die wall
friction can lead to a reduction in the densification rate and to
inhomogeneous densification. This problem can be alleviated
by

 Reducing the reaction between the sample and the die walls

 Pressing fairly flat articles

In hot pressing, the pressure may cause the microstructure to

evolve in an anisotropic manner. The most common effects are
preferential orientation of the grains or enhanced grain
growth in a specific direction. These effects are known as
MT2171/SUA/2023 26
texturing.
Schematic diagram
illustrating the development
of microstructural texturing
during hot pressing

Schematic design of unit

for pressure sintering of
ceramic materials
MT2171/SUA/2023 27
 Hot Isostatic Pressing (HIP)

In hot isostatic pressing, commonly abbreviated as HIP, the

sample is placed in a pressure vessel, the gas pressure is
applied, and the temperature is raised. Achieving the
required pressure at the firing temperature relies on heat up of
the gas by the HIP furnace. A HIP system can be considered to
consist of four basic units,

1) A pressure vessel

2) An internal furnace for heating sample

3) A gas pressurization unit

4) Control Unit

MT2171/SUA/2023 28
 Simplified schematic
diagram of a system
used for a hot isostatic
pressing

Schematic design of a
pressure vessel with a
sample for hot isostatic
pressing
MT2171/SUA/2023 29
Schematic diagram of a system used for a
hot isostatic pressing
MT2171/SUA/2023 30
In most ceramic powders, the HIP
fabrication route involves a initial
powder consolidation using some other
method to form a compact with the
desired shape. Subsequent
densification can be performed by two
routes

i. The powder compact is

encapsulated in a can and then
densified by HIP, Two basic methods
used in hot isostatic
ii. The powder compact is sintered pressing

conventionally to closed porosity

and then densified further by HIP.
MT2171/SUA/2023 31
Compacts with open porosity cannot be densified without
the encapsulation because the pressurizing gas in the
pores resists the sintering stress. The materials commonly
used for encapsulation consist of a thin walled metal (e.g.
Molybdenum or tantalum) can or a glass can. Glass
encapsulation is more economical , particularly when the
compact has complex shape. Gases trapped in the sealed
can may limit the final densification; the system should
be degassed and sealed in a vacuum.

The second route in which the powder compact is sintered

to closed porosity and then subjected to HIP is referred to
as sinter plus HIP or sintering/HIP.
MT2171/SUA/2023 32