[Sintering]

Introduction

The ISO definition of the term ‘sintering’ reads:-

“The thermal treatment of a powder or 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”. In
other words
Sintering is a method for making objects from
powder, by heating the material (below its melting
point) until its particles adhere to each other.
 Introduction

Sintering is traditionally used for manufacturing

ceramic objects, and has also found uses in such
fields as powder metallurgy.
Almost all ceramic bodies and metal powder
compacts must be sintered to produce a
microstructure with the required properties. The
widespread use of the sintering process has led
to a variety of approaches to the subject.
 Types of Sintering
1. Solid state sintering
Only solid phases are present at the
sintering temperature.
2.Liquid phase sintering
Small amounts of liquid phase are
present during sintering.
3. Reactive sintering
Particles react with each other to form
new product phases.
 Important Parameters in
Sintering
These parameters can be divided into four broad
categories:
1. Powder preparation:
-- Particle size
-- Shape
-- Size distribution
2. Distribution of:
-- Second phases
 Important Parameters in
Sintering
3. Powder Consolidation:
-- Green density
-- Pore size distribution
4. Firing/Sintering:
-- Heating rate
-- Temperature
-- Time
-- Applied pressure
-- Atmosphere
 Important Parameters in
Sintering
 Some parameters, such as the sintering
temperature, sintering time, applied pressure,
average particle size and atmosphere can be
controlled with sufficient accuracy.
 Others, such as the powder characteristics and
particle packing are more difficult to control but
have a significant effect on sintering.
 What Happens During Sintering?

 Atomic diffusion takes place and the

welded areas formed during compaction
grow until eventually they may be lost
completely.
 Recrystallisation and grain growth may
follow, and the pores tend to become
rounded and the total porosity, as a
percentage of the whole volume tends to
decrease.
 Driving Force for Sintering

As with all processes, sintering is accompanied

by an increase in the free energy of the system.
The sources that give rise to the amount of free
energy are commonly referred to as the driving
forces for sintering. The main possible driving
forces are:
The curvature of the particle surfaces
An externally applied pressure
A chemical reaction
 Driving Force for Sintering
Schematically it can be shown as
 Stages of Sintering

Three stages are distinguished in sintering

 First Stage
After burn out of any organic additives,
two things happen to the powder
particles when the mobility of the
surface atoms has become high enough;
initially rough surface of the particles is
smoothed and neck formation occurs.
 Stages of Sintering

 Second Stage
Densification and pore shrinkage. If grain
boundaries are formed after the first stage,
these are new source of atoms for filling up the
concave areas which diminishes the outer
surface of the particle.
 Third Stage
Grain growth takes place, the pores break up
and form closed spherical bubbles.
 Mechanisms of Sintering

Six distinct mechanisms can contribute to the

sintering of a consolidated mass of crystalline
particles:
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
Mechanisms of Sintering
 Liquid Phase Sintering

 During liquid phase sintering a liquid phase

coexists with a particulate solid at the
sintering temperature
 The wetting liquid provides a capillary
force that pulls the solid particles together
and induces particle re-arrangement.
 The second phase chosen has lower
melting temperature than the main
constituent.
 Liquid Phase Sintering

 The sintering temperature is set just above

the melting point of the added phase so that
during sintering it forms a liquid phase that
wets the solid particles.
 The pores in the compact are largely
surrounded by the liquid phase and the
driving force for sintering is liquid surface
energy.
 With high liquid fractions, full density can be
achieved almost entirely by rearrangement.
 Liquid Phase Sintering
Grain boundary ‘wetting’ breaks the
polycrystalline particle into single crystal particles
in the initial stages of liquid phase sintering.
These single crystal particles then spheroidize
and coarsen.

Polycrystalline
particle

Liquid
 Liquid Phase Sintering

Wetting is a very important phenomena

which is happening during LPS.
Figure represents the surface tensions of a
multi-phase junction as vectors drawn
parallel to the respective surfaces.
γlv
γsv θ
γsl
 Liquid Phase Sintering

The surface energies for different interfaces is given by

γsl = solid/liquid
γsv = solid/vapor
γlv = liquid/vapor
The vectors representing these surface energies must
balance at the three phase triple junction. The equation
representing this balance is known as “Youngs’ equation”;

sv  sl  cos( )lv

 Liquid Phase Sintering

Grain boundary
Grain B
wetting during LPS γBL
θB
occurs when θA and θB Liquid
γAB θA
approach zero γAL
Grain A

AB  BL cos(B)  AL cos(A)

 Examples of LPS

 Powder Metallurgy parts

-- Copper/Tin alloys
-- Iron/Copper structural parts
--Tungsten Carbide/Cobalt cemented
carbides
 Ceramics
-- Silicon Nitride with a glassy liquid phase
(2wt% alumina + 6wt% yttria)
-- SiC with Silicon liquid phase
 Reactive Sintering
 Two or more constituents in a compact react
during sintering to form a new phase or
phases.
 The reaction is normally exothermic and can
contribute to an enhancement of sintering.
 In some cases the reaction is so exothermic
that it can generate sufficient heat to cause
self-sintering without external heating except
that required for initiating the reaction.
 Reactive Sintering

 This is the basis of combustion synthesis

which if properly controlled can produce a
relatively dense compact of the
synthesized reaction product.

Example of reaction sintering is

3TiO2 + 4AlN → 2Al2O3 + 2TiN + N2

 Sintering Procedure

-- The green compact is placed on a mesh belt and

moved slowly through the sintering furnace.
-- In the preheat zone, the lubricant volatilizes,
leaves the part as a vapor, and is carried away by the
dynamic atmosphere flow.
-- The temperature within the furnace rises slowly
in the preheat zone until reaching the actual sintering
temperature.
-- It remains essentially constant during the time at
that temperature, and proceeds into the cooling zone
where the drop in part temperature is controlled.
 Sintering Procedure

Schematically
 Sintering Procedure

 As the parts travel through the furnace,

the temperature cycle results in changes in
composition and microstructure.
 In the hot zone metallurgical bonds
develop between particles and solid state
alloying takes place.
 The microstructure developed during
sintering determines the properties of the
part.
 Sintering Atmospheres
 The operation is almost invariably carried out
under a protective atmosphere, because of
the large surface areas involved, and at
temperatures between 60 and 90% of the
melting-point.
 These are essential for almost all sintering
processes, to prevent oxidation and to
promote the reduction of surface oxides.
 In practice dry hydrogen, cracked ammonia,
and partially combusted hydrocarbons are
mainly used
 Sintering Atmospheres
 Although the first named is often precluded
because of cost. It is however, used for
sintering carbides and magnetic materials of
the Alnico type.
 It can replace pure hydrogen for many
applications at approximately one-third the
cost, with the obvious exceptions where
reaction with nitrogen cannot be tolerated.
 It is particularly useful for sintering iron, steel,
stainless steel, and copper-base components.
 Advantages of Sintering

1. the possibility of very high purity for the starting

materials and their great uniformity
2. preservation of purity due to the restricted nature
of subsequent fabrication steps
3. stabilization of the details of repetitive operations
by control of grain size in the input stages
4. absence of stringering of segregated particles and
inclusions (as often occurs in melt processes)
5. no requirement for deformation to produce
directional elongation of grains
 References

 Ceramic Processing and Sintering by M.N.

Rahaman
 Ceramic Matrix Composites by Richard
Warren
 Ceramic Fabrication Technology by Roy. W.
Rice
 The Inorganic Chemistry of Materials- How
to Make Things Out of Elements by Paul J.
Van Der Put
 References

 Liquid Phase Sintering by Randell M.

German-Technology
 Blake Concise Dictionary
 Wikepedia-the Free Encyclopedia
 www.azom.com
 www.mse.mtu.edu
 www.epma.com