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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.
(Barsoum, 1997)
Sintering happens naturally in mineral deposits or as a
manufacturing process used with metals, ceramics, plastics, and
other materials.
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?
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
without with
reaction reaction
Types of sintering
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.
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
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
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
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
Sintering mechanisms
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.
neck
green body r2
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
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
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.
= 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
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.
Hipping of silicon nitride improves the final density and as a consequence the
mechanical strength. An improvement of almost 100% is possible.