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Sintering

Heat treatment to bond the metallic particles, thereby


increasing strength and hardness
Usually carried out at 70% to 90% of the metal's
melting point (absolute scale)
The primary driving force for sintering is reduction of
surface energy
Part shrinkage occurs during sintering due to pore size
reduction
Sufficient diffusion must occur during sintering to
ensure a uniform chemistry and structure
Sintering

Sintering I
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. Main goal is how cconsistently to obtain theoretical density at
the lowest possible temperature.

Sintering can occur in the presence


or absence of a liquid phase:
a) Liquid phase sintering
b) Solid phase sintering

(Barsoum, 1997)
Sintering happens naturally in mineral deposits or as a
manufacturing process used with metals, ceramics, plastics, and
other materials.

The atoms in the materials diffuse across the boundaries of the


particles, fusing the particles together and creating one solid piece.

Because the sintering temperature does not have to reach the


melting point of the material, sintering is often chosen as the
shaping process for materials with extremely high melting points
such as tungsten and molybdenum.

An example of sintering can be observed when ice cubes in a glass


of water adhere to each other, which is driven by the temperature
difference between the water and the ice
Sintering Sequence on a Microscopic Scale
(1) Particle bonding is initiated at contact points;
(2) contact points grow into "necks";
(3) pores between particles are reduced in size;
(4) grain boundaries develop between particles in place of necked regions
Metallurgical
Thermodynamically, then, sintering is an irreversible process in which a free energy decrease is
brought about by a decrease in surface area.

physical chemistry :
Sintering is a thermally activated mass transport process which leads to strengthening of
particle contacts and/or a change in porosity and pore geometry accompanied by a reduction of
the free energy. A liquid phase can take part in the process.
What happens during sintering
Why do we need Sintering?
The principal goal of sintering is the reduction of compact porosity. Sometimes the initial
spaces between compacted grains of ceramics are called voids, to differentiate them from the
isolated spaces = pores, which occur in the final stages of sintering.
The sintering process is usually accompanied by other changes within the material, some
desirable and some undesirable.
The largest changes occur in
strength, elastic modulus
hardness, fracture toughness
electrical and thermal conductivity
permeability to gases and liquids average grain number, size and shape
distribution of grain size and shape
average pore size
i and d shape
h
distribution of pore size and shape
chemical composition and crystal structure
Sinteringisawidelyusedbutverycomplexphenomenon.Thefundamentalmechanismsof
sinteringarestillamatterofcontroversy.
Experimentalquantificationofchangesinporefractionandgeometryduringsinteringcanbe
attemptedbyseveraltechniques,
suchas: Dilatometry Buoyancy Gasabsorption Porosimetry Indirectmethods(e.g.
hardness) Quantitativemicroscopy
The description of the sintering process has been derived from model experiments (e.g.
sintering of a few spheres) and by observing powdered compact behavior at elevated
temperatures.
The following phenomena were observed and modeling was attempted:
increase of interparticle contact area with time
roundingoff
g of sharp
p angles
g and p points of contact
in most cases, the approach of particle centers and overall densification decrease in volume of
interconnected pores continuing isolation of pores grain growth and decrease in volume of
isolated pores
The development of microstructure and densification during sintering is a direct consequence
of mass transport through several possible paths (one of these paths is usually predominant at
any given stage of sintering):
GAS phase (evaporation/condensation)
LIQUID phase (solution/precipitation)
SOLID phase (lattice diffusion)
INTERFACES (surface
( f d ff
diffusion, grain boundary
b d d ff
diffusion)
)
VISCOUS or PLASTIC FLOW, under capillary pressure (internal) or externally applied pressure
(pressuresintering, hotpressing, hotisostaticpressing)
What Happens During Sintering?
WhatHappensDuringSintering?

Atomic diffusion takes place and the


welded areas formed during compaction
grow until eventually they may be lost
completely.
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.
decrease
What Happens During Sintering?
WhatHappensDuringSintering?

In the pressing operation the powder


particles are brought together and
deformed at the points of contact.
At elevated temperature the sintering
temperature the atoms can move more
easily and quickly migrate along the
particle surfaces (the technical term is
Diffusion).
What Happens During Sintering?
WhatHappensDuringSintering?

Metals consist of crystallites


At the sintering temperature new crystallites
form at the points of contact so that the
original interparticle boundaries disappear,
or become
b recognizable
bl merelyl as grain
boundaries (This process is called
Recrystallisation).
What Happens During Sintering?
WhatHappensDuringSintering?

The total internal surface


area off the
h pressedd body
b d is
i
reduced by sintering.
Necklike junctions are
f
formed b
between adjacent
particles as can be seen on
the adjoining scanning
electron micrograph.
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.
Sintering
In the sintering operation, the pressed-powder
compacts are heated in a controlled atmosphere to right
below the melting point
Three stages of sintering
Burn-off (purge)- combusts any air and removes lubricants or
binders that would interfere with good bonding
High-temperature- desired solid-state diffusion and bonding
occurs
Cooling period- lowers the temperature of the products in a
controlled atmosphere
All three stages must be conducted in oxygen-free
conditions of a vacuum or protective atmosphere.
Sintering
Sintering atmospheres
Hydrogen (>95%)
Vacuum (low and high)
Inert (Ar, in some cases N2)
Air (only for firing oxide ceramics)
Endogas (30-50%H2, 18-25%CO,
28-48%N2, <0.01%H2O)
heating isothermal sintering
period heating isothermal sintering
period
intermed.
stage
Shrinkage, density

initial

temperature
stage

time time
Development of density and shrinkage Temperature evolution during a simple
during a simple sintering cycle sintering cycle.
Chemical doping,
Atmospheric control
An appropriate time/temperature cycle

Hence, there is strong dependence of sintering kinetics on nature and


amount of uncontrolled impurities, dopants and sintering aids.
Solid state sintering and liquid phase sintering. (transient liquid phase sintering and viscous flow sintering)
Solid state sintering occurs when the powder compact is densified wholly in a solid state at the sintering
temperature, while liquid phase sintering occurs when a liquid phase is present in the powder compact
during sintering.
At temperature T1, solid state sintering occurs in an AB
powder compact with composition X1, while at
temperature T3, liquid phase sintering occurs in the
same powder compact.
Viscous flow sintering occurs when the volume fraction
of liquid is sufficiently high, so that the full densification
of the compact can be achieved by a viscous flow of
grainliquid mixture without having any grain shape
change during densification.
Transient liquid phase sintering is a combination of liquid
phase sintering and solid state sintering. In this sintering
technique a liquid phase forms in the compact at an
early stage of sintering, but the liquid disappears as
sintering proceeds and densification is completed in the
solid state. AB powder compact with composition X1 is
sintered above the eutectic temperature but below a
solidus line, for example at temperature T2.
Since the sintering temperature is above the AB
eutectic temperature, a liquid phase is formed through a
reaction between the A-B during heating of compact.
During sintering, however, liquid phase disappears and
only a solid phase remains because equilibrium phase
under given sintering condition is a solid phase
Sintering

solid state sintering liquid state sintering pressure assisted sintering

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


phasic phasic <15% >15% pressing pressing

without with
reaction reaction
Types of sintering

Solid-state sintering (SSS)


only in high-purity compounds
Liquid phase sintering (LPS)
<20% liquid; impurities or specific additives
Viscous glass sintering or viscous flow (VGS)
Densification of glass powders
Viscous composite sintering or vitrification (VCS)
>20% liquid: whitewares, porcelains
Figure shows typical microstructures of partially sintered powder compacts without (a) and with
(b) a liquid phase. In both cases, sintering has proceeded to the final stage in which pores are
isolated. Such an isolated pore stage is generally reached quickly at usual sintering
temperatures. The elimination of isolated pores is more time consuming and utilizes almost all
of the sintering time.
Consider first the motivation for sintering, i.e., the source of the lowering of free
energy which occurs in this as in every other irreversible process.
There seem to be two possible motivations: pressure and surface tension.
Two particles which are being pressed together by an external force can yield to the
force by growing together. This may be important in the earliest stages of sintering of
compacts which have been compressed before hand and may be important
throughout the whole sintering process when pressure is applied simultaneously with
heating.
In other cases surface tension is probably the principal motivation: the growing
together of particles and the shrinking of cavities decrease the total surface area and
therefore decrease the total surface free energy.
There seem to be four possible types of mechanism by which the transport of
matter involved in sintering may take place: plastic or viscous flow, evaporation
and condensation, volume diffusion, and surface migration.
Basic to any theory of sintering is a knowledge of the laws by which the rates of
these four mechanisms are determined by the configuration of the particles
being sintered through the motivations of surface tension and stress.
Most of the sections to follow will be devoted to a phenomenological theory of
the way in which the rates of the transport mechanisms are influenced by
surface-tension effects; the motivation of diffusion by pressure.
Metallurgy and solid state physics
Diagram of particles in sintering showing possible movements of atoms
Sintering: removal of pores between particles accompanied by
shrinkage (densification) and grain growth.

Driving force for sintering: reduction of surface area and lowering of


surface energy.
High energy solid-gas surfaces are replaced by low energy solid-solid
interfaces (grain boundaries).

At microscopic level, the driving force is related to the difference in


surface curvature and consequently of partial pressure and chemical
potential between different parts of the system.

Neck formation Pore removal and


shrinkage

Effect of particle size: the smaller the particles, the higher the radius of curvature and the chemical
potential higher sintering rate.
Very small particles with high surface area also have high surface free energy and thus
have a strong thermodynamic drive to decrease their surface area by bonding together.
Stages of sintering
(a, b) Initial stage sintering. Formation of strong
bonds and necks between particles at the contact
points. Moderate decrease of porosity (initial 40-
50%) from particle rearrangement.
(c) Intermediate stage sintering. The size of the
necks increases and the amount of porosity
decreases. The sample shrinks (the centers of the
grains move towards each other. The grains
transforms from spheres to truncated octahedra
This stage continues until pores are closed (r.d.
90%).
(d) Final stage sintering. Pores are slowly
eliminated and major grain growth
can occur.

Initial stage Intermediate stage Final stage


Sintering stages

Initial stage: Transport from high energy convex particle surfaces to


concave surfaces, necks. Fusing, increased contact area. Pore volume
and density remains almost constant (4-5% shrinkage, relative density
0.5-0.6)
Intermediate stage: Inter-particle neck growth, grain boundary area
increase, inter-particle grain boundary flattens, pore diameters
decrease. (5-20% shrinkage, relative density up to 0.95)
Final stage: isolated pores may remain at triple points or inside grain
matrix. These pores may be gradually eliminated. (relative density >
0.95)
The development of microstructure and densification during
sintering is a direct consequence of mass transport through several
possible paths
(one of these paths is usually predominant at any given stage of
sintering):

GAS phase (evaporation/condensation)


LIQUID phase (solution/precipitation)
SOLID phase (lattice diffusion)
INTERFACES (surface diffusion, grain boundary diffusion)
VISCOUS or PLASTIC FLOW, under capillary pressure (internal) or
externally applied pressure (pressure-sintering, hot-pressing, hot-
isostatic-pressing)
Sintering and grain growth
Effect of curvature on thermodynamic properties
Laplace equation for a spherical droplet

r 2 Pressure difference across a curved


P = interface. For a planar surface, P = 0
r r (micron) P/P(r=)

Effect of curvature on vapour pressure (Thomsons equation) 1 1.002


0.1 1.02
P V 2 V: molar volume 0.01 1.21
ln = If r > 0, P > P(r=)
P(r = ) RT r : surface tension 0.001 7.03

r For a cavity (r < 0), P


Grain
< P(r=) Pore
Positive curvature

Negative curvature
Effect of curvature on chemical potential
2 Grain
i i (r = ) = Vi Nul curvature
r
Ostwald ripening Particles with different curvature have different vapour
1 1 r1 r2 pressure and chemical potential. Therefore they are not in
i (r1 ) i (r2 ) = Vi 2 equilibrium and the larger one will grow at the expense of
r1 r2 the smaller one.
Sintering carried out in three stages:
First stage:
Temperature is slowly increased so that all volatile materials in the
green compact that would interfere with good bonding is removed
Rapid heating in this stage may entrap gases and produce high internal
pressure which may fracture the compact

Second stage: High temperature stage


Promotes solid-state bonding by
diffusion.
Diffusion is time-temperature
sensitive. Needs sufficient time

Third stage:
Sintered product is cooled in a
controlled atmosphere
Prevents oxidation and thermal shock
Promotes vapour-phase
transport
Because material heated close to
MP, metal atoms will be released
in the vapour phase from the
particles
Vapour phase resolidifies at the
interface
What happens during sintering?
Particle to particle bond
Elimination of pores
Shrinkage
Densification
Grain growth

Grain growth
The driving force for sintering is a reduction in the system free energy,
manifested by decreased surface curvatures and an elimination of
surface area.
Sintering can occur with or without densification, i.e. shrinkage, as
evidence by the inter-particle neck growth.
driving force for sintering
Surface energy I
The macroscopic driving force operative during sintering is the reduction of the excess energy
associated with surfaces. This can happen by (1) reduction of the total surface area by an
increase of the particle size and/or (2) by the elimination of solid/vapor interfaces and the
creation of grain boundaries.

Surfaces can be characterize according to their curvature and the resp. radius of curvature:

view direction

flat concave
r
r convex

radius: infinite negative positive

Extending a surface or changing the


radius of curvature of a surface requires The surface energy is
work: defined as the increase in free
energy G per new surface A
formed.

soap film
G
blow E = (1)
in that A
direction
Surface energy II
The excess surface free energy is due to the different atomic arrangements along the
surface relative to the bulk arrangement:

view direction

flat concave
r
r convex

Atom bonded to 6 neighbors

Atom bonded to 5 neighbors

Atom bonded to 4 neighbors

Atom bonded to 2 neighbors

The average bonding of an atom is decrasing from concave over flat to convex
surfaces, the partial pressure over the surfaces is increasing in the same
Bondingmechanismsduringsinteringarecomplicatedanddifferent,howeverthemaindriving
force that enacts this particle bonding is considered to be a reduction of energy due to a
forcethatenactsthisparticlebondingisconsideredtobeareductionofenergyduetoa
reducedsurfacearea.Powderswithagreatersurfaceareawillhaveahigherdrivingforce
towardsbondingandaloweringofthispotentialenergy.
Alloyingofdifferentmetalpowdersalsooccursduringsintering.Thesinteringtemperaturemust
alwaysbelowerthanthemeltingtemperatureofatleastoneofthepowderconstituents.In
somecases,thesinteringtemperatureisabovethemeltingpointofoneofthematerialsbut
belowthemeltingpointoftheother.Thisiscalledliquidphasesintering.Liquidphasesintering
gp q p g q p g
caneliminateporosityandproducepartswithexcellentmaterialproperties.
The main driving force is excess surface free energy in solid state sintering. The surface energy
can be reduced by transporting material from different areas by various material transport
mechanisms so as to eliminate pores.
material transport during solid state sintering occurs mainly by surface transport, grain
boundary transportation. This surface transport can be through adhesion, surface diffusion.
Many models available to describe sintering process like viscous flow, plastic flow, grain
boundary and volume diffusion models. These models will be briefly described here.
Microstructure (NiAl SiC)
Microstructure(NiAlSiC)

reinforcement

matrix

g
grain

grainboundary

interface

3
Grains and Grain Contacts
GrainsandGrainContacts

connectivity=4

4
Sinter Bonding
SinterBonding

5
Porosity
voidsbetweenparticlesorgrains
missing volume
missingvolume
oftengivenasvolumepercent
10%porosity=90%dense
no mass no strength no hardness
nomass,nostrength,nohardness
generallydegradesproperties
usefulinfilters

6
Three Phases
ThreePhases

TiC
toolsteel
l l
(Ferrotic)
pore

7
Coordination Number
CoordinationNumber
threedimensionalnumberofcontacts
orderedpacking
ordered packing 4,6,8,12(diamond,cubic,
4, 6, 8, 12 (diamond, cubic,
bodycenteredcubic,facecenteredcubic)
randommonosizedspheres=60%dense,7
d i d h 60 % d 7
contacts
fulldensitygrains=100%dense,12to14
contacts

8
Polycrystalline

fulldense
alumina
connectivity=6

9
Surface diffusion leads to
particle coarsening,
instead of shrinkage

Only lattice diffusion (at


final stage) and GB
diff i
diffusion (
(mostly
tl i
in
intermediate stage) leads
to densification.
Theoretically, if all pores in a compact are very small, full densification
can be achieved without grain growth; otherwise, grain growth is
inevitable during sintering to obtain full densification.
In the final-stage sintering, the elimination of isolated spherical pores is difficult
since vacancies must diffuse to distant grain boundaries, which is a very slow
process. Also, with prolonged sintering, pore coarsening causes the mean pore size
to increase while the number of pores decreases.
GBD and LD are important densification mechanism in metals and
ceramics. Plastic flow by dislocation motion in response to sintering
stress plays essentially no role in the sintering of ceramics because of
the low dislocation density. (Ceramics do not have the dislocation mobility of metals because
of different atomic bond types, because of the sintering process (pores) and the formation of intercrystalline
phases (structural imperfections).

Due to the presence of grain boundaries in polycrystalline materials,


the energy decrease due to elimination of free surface area does not go
totally into driving the densification process. Part of the energy decrease
goes into driving the grain growth process, leading to reduction in
driving force for densification.

The presence of grain boundaries also dictates the equilibrium shapes


of the pores (and grains) which can influence matter transport during
sintering.
Mechanism Source Sink Densification Any mechanism in which the source of
material is the surface of the particles and the
Surface diff. Surface Neck No sink is the neck area cannot lead to overall
densification, because such a mechanism
Evaporation- Surface Neck No
does not allow the particle centers to move
condensation
closer together.
Volume diff. Grain Neck Yes For densification to occur, the source of the
boundary material has to be the grain boundary or
Grain boundary Grain Neck Yes region between powder particles, and the
diffusion boundary sink has to be the pore or the neck region.

Sintering mechanisms

Surface diffusion &


evaporation-condensation

Volume and grain boundary


diffusion

Positive curvature

Negative curvature

Nul curvature
Mechanisms of Sintering
In crystalline solids matter transport occurs by diffusion of atoms, ions
or molecules along definite paths that define the mechanisms of
sintering. Viscous flow is the dominant sintering mechanism in glass.
Sintering of crystalline material can occur by at least six
mechanisms/paths:
Vapour transport (evaporation-condensation), Surface diffusion
Lattice (volume diffusion), Grain boundary diffusion, Plastic flow
A distinct is commonly made between densifying and non-densifying
mechanism.
Vapour transport, Surface diffusion, Lattice diffusion from the particle
surfaces to the neck lead to neck growth and coarsening of the particles
without densification.

The densifying mechanisms Grain boundary diffusion and lattice


diffusion from the grain boundary to the neck, and plastic flow cause
neck growth as well as densification (shrinkage).
When the non densifying mechanism dominate, coarsening leads to the
production of a porous article, whereas a dense article favoured
under the conditions when the densifying mechanism dominate.
(a) all porosity has been removed during sintering in which the densifying processes dominate.
(b) The sintering where coarsening mechanisms dominate results in formation of a continuous
network of solid material (white) and porosity (black).
(black) The microstructural change is not
accompanied by any densification.
Sintering is, therefore, said to involve a competition between densification and coarsening. The
production of ceramics with high density (Fig. a) would require choosing the sintering conditions
so that the non densifying mechanisms are not very active.
When coarsening mechanisms dominate, the production of a highly porous body is favored
(Fi b)
(Fig.b).
Mechanism in solid state sintering
As discussed earlier, material or atom transport forms the basic mechanism for sintering
process. A number of mechanisms have been proposed for sintering operation.
These are,
1. Evaporation condensation, 2. diffusion (can be volume diffusion, grain boundary
diffusion, surface diffusion), 3. viscous flow, 4. plastic flow
1. Evaporation and condensation mechanism
The basic principle of the mechanism is that the equilibrium vapor pressure over a
concave surface (like neck) is lower compared to a convex surface (like particle
surface). This creates the vapor pressure gradient between the neck region and
particle surface. Hence mass transport occurs because of vapor pressure gradient
from neck (concave surface) to particle surface (convex surface). The driving force
of this is based on Gibbs-Thomson equation, -0 = RT ln(p/p0) = (-)()/r where
and 0 are chemical potentials of initial and final surfaces, R is universal gas
constant, T is temperature in K, p and p0 are partial pressures over the curved and
flat surface respectively, is the surface free energy, is the atomic volume

R. Ganesh Narayanan, IITG


2. Diffusion mechanism
- Diffusion occurs because of vacancy concentration gradient. In the case of two
spheres in contact with each other, a vacancy gradient is generated between the two
surfaces. This condition can be given by, -0 = RT ln(C/C0) = (-)()/r Where C
and C0 are the vacancy concentration gradient around the curved and flat surface.
- Kuczynski has derived empirical relation for neck growth rate for the following two
cases, i) a sphere in contact with flat surface the rate of neck growth is
proportional to seventh root of time (t1/7), ii) when two spheres are in contact the
neck growth rate is, x5/a2 = 40 D.t/RT where a radius of sphere, D volume
diffusivity of material, atomic or molecular volume.
- Neck growth due to surface diffusion, lattice diffusion, vapour transport, grain
boundary transport from GB source, lattice diffusion from sources on GB, lattice
diffusion from dislocation sources
3. Viscous flow mechanism
According to this concept, sintering occurs due to the presence of lattice vacancies. This
is important in sintering of glass. Frenkel developed the equation, (x2/a) = 3/2 (/).t
where x is the neck radius & a is the radius of particle. Increasing the temperature
results in increased plasticity of metal powders. Balshin proposed the following
R. Ganesh Narayanan, IITG
mechanisms to happen during sintering.
1. Particle rearrangement, 2. particle shape change, 3. grain growth.
Frenkel suggested that surface tension lead to sintering and solids could behave like
newtonian liquids at high temperatures i.e., sintering occurs by viscous flow. He
derived an equation for the viscosity coefficient, = kT/D where k is the
Boltszmans constant, T is the absolute temperature, D is the self-diffusion
coefficient, is the atomic volume. He derived an expression on neck growth
during sintering of two spherical particles of radius a with time t as, x2 = 3a/2
where x is the neck radius and is the surface energy.
4. Plastic flow mechanism
Bulk flow of material by movement of dislocations has been proposed as possible
mechanism for densification during sintering. Importance was given to identify
dislocation sources during the sintering process. Even if frank read sources are
present in the neck region, the stress available for dislocation generation is very
small, indicating that the generation of dislocation must come from free surfaces.
Only if the surface is very small of the order of 40 nm, the stress required for
dislocation generation will be sufficient. But experimental results have shown
the absence of applied stress and plastic flow is expected to occur during early
stages of sintering. Plastic flow mechanism is predominant during hot pressing.
R. Ganesh Narayanan, IITG
r1
B

neck

green body r2

r1 >> r2 (r2 is negative!)

Due to the fine nature of the powders used as raw materials,


the green bodies have a high internal surface area and,
r3 therefore, a high excess surface free energy. During the
r3 >> r4 heat treatment the internal surface will be reduced and the
necessary material movement is driven by the differences in
surface curvature

A) between different sized grains, the big grains getting


r4 bigger, the small ones disappear = grain growth/shrinkage
= overall coarsening of the texture

B) between the surface of two grains and the neck region


between them = elimination of pore volume = densification
Material moves to the neck regions of a polycrystalline solid
because of the vapour pressure differences between the convex
grain surfaces//grainboundary at the contact and the concave
shaped necks.
Neck
P: difference in
P < 0 P < 0 vapour pressure rel.
Material flux to flat surface.

P > 0 P > 0
Vacancy flux
Conc. vacancies higher
than within the grains
Diffusion is driven by a vacancy concentration gradient:

where Co is the equilibrium vacancy concentration, is the surface energy, is the atomic
volume, k is Boltzmann constant, and T is the absolute temperature.
The net impact of grain boundary diffusion depends on the grain size or
the number of grain boundaries per unit volume.
As surface area is consumed and surface diffusion decline in
importance, the simultaneous emergence of new grain boundaries
increases the role of grain boundary diffusion.
Pores can like grains grow or shrink. The two parameters affecting pore
growth is the number of surrounding grains and the dihedral angle.
Generally pores with few neighboring grains tend to shrink.

pore pore

(Small) pores with few neighboring


grains have concave surfaces and tend
to shrink, whereas (large) pores with
many neighboring grains have convex
surfaces and tend to grow

Monodisperse greenbody of boron doped SiO2.


The larger pores may be difficult to
evacuate.
A pore and a grain boundary
have a binding energy because
the pore reduces the total grain
boundary area.

The binding energy decrease


during densification.

Grain growth forces the grain


boundary to be curved, leading
to a progressive increase in grain
boundary area as the grain
boundary bows to sustain
contact with a slower moving
When a critical condition is achieved, it is favorable pore.
for the boundary to break away from the pore.
Separation leads to elimination of grain boundary
bowing and the drag force on the boundary. Grain
boundary mobility increases.
When porosity is high, there is a penalty for pore-
boundary separation.
Densification reduces that penalty.
Sintering and grain growth
Grain growth
m
General relationship: d m d0 = k t m = 2-3

Grain growth in undoped and Mg-doped alumina

Dopants in solid solution affect depress


grain growth because they segregate at
grain boundaries reducing:
- the interfacial energy
- the grain boundary mobility

Grain growth is inhibited by pores, second phase inclusions and solid solution impurities. Pores and
solid inclusions act as pinning centres for weakly curved grains. The critical grain size at which grain
growth stops is given by (Zener):
di
Df
Vi
Df: limiting grain size
di: diameter of inclusions
Vi: volume fraction of inclusions

Dragging and agglomeration of pores


Grain boundary pinned by
determined by grain boundary
a pore
migration
Factors influencing sintering
(a) the initial density of the compacts,
(b) temperature,
(c) time,
(d) the mechanism of sintering,
(e) the average particle size, and
(f) the size distribution of the powder particles.

Particle size: Materials transport over smaller


distances, higher surface energies. Larger grains grow
at the expense of smaller ones. Coarsening of the
grains.
Particle packing: Improves the number of contact
points between particles. Relative density increased.
Faster densification, less volume shrinkage.
Particle shape: Irregular shaped particles with higher
surface area/volume ratio, have a higher driving
force for sintering.
Particles that pack poorly sinter poorly
The mechanisms active at each sintering stage are different and have to be described by
separate kinetic model. The general form of the shrinkage (= densification) equation in the
initial stage can be given as

L const t n r: particle radius m: 1-1.5


= t time (n: 1/3 -2/5)
L kT r m L: length of the sintered body
It is obvious from the above equation that material with small grain size will shrink
e.g. densify much faster than coarse green bodies.

Densification and grain growth occur simultaneously. The resulting textures


and density depend on which mechanism is predominant.

a) densification followed by grain growth b) Coarsening alone


Only densification followed by grain
growth will give good final densities.

Fast firing and doping of


the starting material are
ways to suppress grain
growth
Difference in densities and grain sizes in fast fired
and and conventionally sintered alumina
Property changes during sintering
Densification is proportional to the shrinkage or the amount of pores removed in
the case of single component system
IN multicomponent system, expansion rather than shrinkage will result in
densification and hence densification can not be treated as equal to the amount of
porosity removed.
densification results in mechanical property change like hardness, strength,
toughness, physical properties like electrical, thermal conductivity, magnetic
properties etc. Also change in composition is expected due to the formation of solid
solution.
100
density
Indicated property
compared to solid strength
material, %
ductility

0 R. Ganesh Narayanan, IITG


Time
Liquid phase sintering

Second phases, that melt at the sintering temperature, are often present as impurities in the
starting powder or a added on purpose. The small amount of liquid present during sintering
will significantly alter the kinetics and the properties of the sintered body.
It enhances the rate of sintering and the homogeneity of the final sinter body.

Microstructure of as-sintered SiC


with gadolinium and holmium
oxides. The oxides were liquid
during the sintering and were
quenched to a glass
Liquid phase sintering

Enough liquid phase must be present (1-5 vol.%).


The liquid must wet the solid (contact angle <<90).
The solid must be partially soluble in the liquid.
Driving forces are higher for small particles (stronger capillary forces) with high
surface energy and high solubility

> 90: nonwetting < 90: wetting

= 0: spreading
Liquid phase sintering
For certain materials, such as cemented carbides or hardmetals, a sintering mechanism involving
the generation of a permanent liquid phase is applied. This type of liquid phase sintering
involves the use of an additive to the powder, which will melt before the matrix phase and
which will often create a so-called binder phase. The process has three stages:

Rearrangement As the liquid melts, capillary action will pull the liquid into pores and
also cause grains to rearrange into a more favourable packing arrangement

Solution-precipitation In areas where capillary pressures are high, atoms will preferentially go
into solution and then precipitate in areas of lower chemical potential where particles are not
close or in contact. This is called contact flattening and densifies the system in a way similar to
grain boundary diffusion in solid state sintering. Ostwald ripening will also occur where smaller
particles will go into solution preferentially and precipitate on larger particles leading to
densification.

Final densification Densification of the solid skeletal network, liquid movement from efficiently
packed regions into pores. For permanent liquid phase sintering to be practical, the major phase
should be at least slightly soluble in the liquid phase and the binder additive should melt
before any major sintering of the solid particulate network occurs, otherwise rearrangement of
grains will not occur.
Transient liquid phase sintering
In a compact that contains only iron powder particles, the solid state sintering process
would generate some shrinkage of the compact as the sintering necks grow.
However, a common practice with ferrous PM materials is to make an addition of fine
copper powder to create a transient liquid phase during sintering.

At sintering temperature, the copper melts and then diffuses into the iron powder
particles creating swelling. By careful selection of copper content, it is possible to
balance this swelling against the natural shrinkage of the iron powder skeleton and
provide a material that does not change in dimensions at all during sintering. The
copper addition also provides a useful solid solution strengthening effect.
Reactive sintering

In polyphase ceramics, sintering can be accompanied by chemical


reaction. Examples:

Alumina and titaniumnitride based cutting tools

AlN + TiO2 = Al2O3 + TiN (under N2 atmosphere)

The advantage over direct sintering of the final products is, that TiN, a
conducting material, forms a continous network through reactive
sintering, allowing machining through electroerosion.

Aluminiumtitanate (low thermal expansion coefficients) for thermal shock


application

Al2O3 + TiO2 = Al2TiO2


Aluminiumtitanate is used as exhaustpipe connectors (Porsche 944)
Hot-Isostatic Pressing
HIP is use to
Densify existing parts
Heal internal porosity in casting
Seal internal cracks in a variety of products
Improve strength, toughness, fatigure resistance,
and creep life.
HIP is relative long, expensive and unattractive
for high-volume production
Hot-Isostatic Pressing
Hot-isostatic pressing (HIP) combines powder compaction
and sintering into a single operation
Gas-pressure squeezing at high temperatures
Heated powders may need to be protected from harmful
environments
Products emerge at full density with uniform, isotropic
properties
Near-net shapes are possible
The process is attractive for reactive or brittle materials, such
as beryllium (Be), uranium (U), zirconium (Zr), and titanium
(Ti).
Hipping of Si3N4

sinter mode sinter aid % of theoretical mechanical strenght


S: normal appearance density reached
HP: hipping of a liquid

Hipping of silicon nitride improves the final density and as a consequence the
mechanical strength. An improvement of almost 100% is possible.