Sintering

MEEN40080: Technical Ceramics

Kevin Roche BE, PhD
School of Mechanical and Materials Engineering
University College Dublin

1
This section

• Sintering and microstructure

• Conditions for
• Solid-state sintering
• Liquid phase sintering
• Sintering kinetics
• Dilatometer
• Coarsening and densification

Also refer to Fundamentals of Ceramics Chapter

10:
http://library.ucd.ie/iii/encore/record/C__Rb2551404 2
 Powder processing route
• Technical ceramics need carefully controlled
production processes to achieve high quality
• homogenous chemistry and microstructure
• minimal porosity and other flaws
• Dimensional accuracy
• Each step contributes to this

Link to video of green machining and shrinkage

Example powder processing route for a
https://youtu.be/Ev02IOPY1B8?si=1oVyBM-UNTZ sialon ceramic
L2va_ N. Ichinose, editor. Introduction to Fine Ceramics: Applications
in Engineering. Wiley, Chichester, UK, 1987.
3
 Sintering and microstructure
Some material properties and the microstructure required to obtain them. The microstructure is
highly dependent on initial particle size and the sintering process

Effect of porosity on compressive strength for some

ceramics
Reminder of commercial ceramics and example applications:
https://www.ceramtec-industrial.com/en/materials
4
Sintering
• “…any change of shape which a small particle C. Herring 1950 J. Appl. Phys. 21:301-303

or cluster of particles of uniform composition

undergoes when held at high temperature”

• Driving force is the minimisation of the free

energy of the system, mostly by reducing
surface energy
• Driving force is small: J/mol compared to
kJ/mol for chemical reactions Schematic of idealised sintering where each particle becomes one
grain in the solid. Grain shape minimises grain boundaries while
eliminating internal pores (surface area), therefore minimising
surface energy

5
Liquid vs solid state sintering
• Solid state sintering
• No liquid present during sintering
• Relies on solid state diffusion
• Advantageous where a glassy grain boundary phase
would be a problem e.g. creep resistance
• Liquid phase sintering
• Some liquid present during sintering, but not
completely molten
• Reactions between components lead to liquid
formation at high temperature
• Faster, more uniform densification than solid-state
• Liquid reduces friction between particles and enables
rearrangement of particles
• More widely applied in industry a) Liquid phase and b) solid phase sintering

• E.g. ferrite magnets, SiN, capacitors, abrasives, more..

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Solid-state sintering
• Driven by energy reduction by:
1. Reduction in total surface area (grain size increases – grain coarsening)
2. Removal of solid-gas interfaces (densification)
• If process 2 is dominant, pores reduce in size and disappear with time, but if process 1 is
dominant pores coarsen with time – fewer but larger grains and pores

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Conditions for solid-state sintering
• Driven by reductions in surface energy – for densification,
grain boundary energy must be less than 2x solid/vapour
surface energy so it is energetically favourable to replace
two solid/vapour surfaces with a grain boundary
• At equilibrium

• where is the solid/solid surface energy (i.e. energy of the

grain boundary), is the solid/vapour surface energy, and is
the dihedral angle of the solid/solid-solid/vapour junction.

Dihedral angle between grain

boundary and solid/gas interface
W. D. Kingery, H. K. Bowen, and D. R. Uhlmann.
Introduction
to Ceramics. Wiley-Interscience, New York, 2nd
edition, 1976.
8
Conditions for solid-state sintering
• If we assume the lowest (theoretically) possible value , the
maximum dihedral angle is 180°, since

• In practice is higher

• For oxides

This implies a limit to the reduction in

porosity during sintering, but what
might you do to reduce it further?

Dihedral angle between grain

boundary and solid/gas interface
W. D. Kingery, H. K. Bowen, and D. R. Uhlmann.
Introduction
to Ceramics. Wiley-Interscience, New York, 2nd
edition, 1976.
9
Conditions for liquid-phase sintering
• Similarly for liquid-phase sintering

• And

Bubble raft ‘sintering’ video: https://www.youtube.com/watch?

v=ah1Q6yqTdpA
(Note this is simplified compared to real sintering Dihedral angle between grain
boundary and solid/liquid interface
processes but still a great visualisation) W. D. Kingery, H. K. Bowen, and D. R. Uhlmann.
Introduction
to Ceramics. Wiley-Interscience, New York, 2nd
edition, 1976.
10
Conditions for liquid-phase sintering
• If then and the liquid (and subsequently glass) is
distributed as pockets at the grain boundary triple-points
(where three grains meet)
• If (i.e. ) then the liquid partially penetrates the grain
boundaries
• If (i.e. ) then the liquid forms triangular prisms at the
triple-points, with penetration of the liquid along any
length of the grain boundary

• Low means high wettability of the solid by the liquid,

which is a requirement for the liquid to accelerate the
densification process
• Liquid needs to fully coat the solid particles to have Dihedral angle between grain
maximum effect boundary and solid/liquid interface
W. D. Kingery, H. K. Bowen, and D. R. Uhlmann.
Introduction
to Ceramics. Wiley-Interscience, New York, 2nd
edition, 1976.
11
Liquid distribution with dihedral
angle

W. D. Kingery, H. K. Bowen, and D.

R. Uhlmann. Introduction
to Ceramics. Wiley-Interscience,
New York, 2nd edition, 1976.

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Sintering kinetics
• Normally measure densification (linear shrinkage of a powder compact with time at a fixed
temperature using a dilatometer

F. Thümmler and R. Oberacker. An Introduction to Powder

Metallurgy. Institute of Materials, London, 1993.
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Sintering kinetics
• Dilatometry does not reveal coarsening: this must be observed by measuring grain size with time
using microscopy
• Curve x is pure coarsening, z is densification followed by grain growth, and y is simultaneous
coarsening and grain growth

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Sintering kinetics
• Typically materials follow curve y
• To obtain near theoretical densities we need curve z – coarsening of grains and pores is
suppressed until most of the shrinkage has occurred
• Once larger pores have formed they become very difficult or impossible to remove
• Following curve x leads to large grains and pores and no longer has the surface free energy to
drive densification, so will remain porous

15
Example – Mg doping in Al2O3
Note
elimination of
porosity first,
followed by
grain growth.

Note also
significant
effect of a
small amount
of Mg addition
leading to
high
theoretical
density

16
Coarsening example
• Fe2O3 sintered in (a) air and (b) HCl
atmosphere
• Note dramatic effect of HCl on shrinkage
and porosity

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 Sintering 2
MEEN40080: Technical Ceramics
Kevin Roche BE, PhD
School of Mechanical and Materials Engineering
University College Dublin

18
This section

• Local driving forces for densification

• Effect of curvature on
• Partial pressure above the surface
• Vacancy concentration below the surface
• Diffusion
• Atomistic models of solid-state sintering
• Coarsening mechanisms
• Densifications
• Kinetics of solid-state sintering

Also refer to Fundamentals of Ceramics Chapter

10:
http://library.ucd.ie/iii/encore/record/C__Rb2551404 19
Sintering
• “…any change of shape which a small particle C. Herring 1950 J. Appl. Phys. 21:301-303

or cluster of particles of uniform composition

undergoes when held at high temperature”

• Driving force is the minimisation of the free

energy of the system, mostly by reducing
surface energy
• Driving force is small: J/mol compared to
kJ/mol for chemical reactions Schematic of idealised sintering where each particle becomes one
grain in the solid. Grain shape minimises grain boundaries while
eliminating internal pores (surface area), therefore minimising
surface energy

Global driving force, but what about

local driving force? i.e. how and why do
the individual atoms move?

20
Local driving forces for densification
• Global driving force is reduction in surface energy
• Locally, this is described through difference in curvature of surfaces. There is a difference in
chemical potential, Δµ, per formula unit MX, between flat and curved surfaces

• Where is the solid/vapour surface energy, is the volume of one formula unit of MX, and is geometry
dependent curvature, e.g. for a sphere of radius ρ,
• This difference in chemical potential will cause atoms to move from the higher to lower potential region

• Two particle considerations relate to the partial pressure above a curved surface and vacancy
concentration under a curved surface

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Effect of curvature on partial
pressure
• For a concave surface ρ (and therefore κ) is negative, and positive for a convex surface. Therefore
the partial pressure of a material is less over a flat surface than over a convex surface, and
greater over a flat surface than over a concave surface (Pconvex > Pflat > Pconcave), i.e., atoms are least
tightly bound to a convex surface, and therefore have greater mobility. (visually most obvious for
the very top atom of the convex surface that is only bonded to one other atom)

22
Effect of curvature on partial
pressure
• At equilibrium, the difference in chemical potential is given by:

• Where k is Boltzmann’s constant and P is the partial pressure above a surface

• Substituting based on surface curvatures gives

• Assuming , we can simplify to

• So for spherical particles of radius ()

Negative if radius of curvature is

negative, leading to the relationship
illustrated on the previous slide

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Effect of curvature on vacancy
concentration
• There is a higher concentration of vacancies under a concave surface than under a convex
surface, creating a driving force for atoms to migrate from peaks (convex surfaces) to troughs
(concave surfaces).
• Consider creating a vacancy at each of the red shaded sites. Under the convex surface, the
surrounding atoms will have fewer bonds on average (will be in higher energy states), and will be
more likely to fill the vacancy. The vacancy is less energetically favourable and less likely to occur,
therefore there are fewer

24
Effect of curvature on vacancy
concentrations
• The equilibrium concentration of vacancies under a flat and stress free surface, C0 is related to
their enthalpy of formation, Q, by

• Where K’ incorporates the entropy of vacancy formation and other constants

• If we consider the effect of the chemical potential of an atom just below a curved surface on the
energy of a vacancy

• Since

25
Diffusion
• Atoms are constantly vibrating with thermal energy
• Some will have enough energy to leave their equilibrium position and move through the
material…this is diffusion
• They will diffuse from regions of high energy towards regions of low energy

26
 Diffusion mechanisms
• For an atom to diffuse, there must be space for
it to move into, three diffusion mechanisms are
show, with the third much less common than
the first two
• (a) Vacancy mechanism – an atom moves to a
neighbouring vacancy (and the vacancy moves in
the opposite direction)
• (b) Interstitial diffusion – interstitial atom moves
to neighbouring interstitial site
• (c) Interstitialcy mechanism – interstitial atom
replaces an atom in a regular site, and the
regular atom is moved to an interstitial site

• In each case the moving atom must overcome

an energy barrier ΔHm (i.e. squeeze through a
small gap)
A vacancy will diffuse faster than an atom, why?

27
Atomistic models of solid-state
sintering
• There are 5 mechanisms by which mass
transfer occurs during solid-state sintering

1. Evaporation-condensation
1. Evaporate from convex surfaces to the
vapour phase and recondense at convex
surface of the neck
2. Surface diffusion
1. Diffusion along the surface of a particle

28
Atomistic models of solid-state
sintering
3. Volume diffusion
1. Surface to neck through the bulk of the grain
2. Grain boundary to neck through the bulk of
the grain

29
Atomistic models of solid-state
sintering
4. Grain boundary diffusion
1. Diffusion along the grain boundary to the
neck

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Atomistic models of solid-state
sintering
5. Viscous flow or creep
1. Movement of particles from areas of high stress to areas of low stress by viscous flow (e.g. in a
glass) or plastic deformation (creep), leading to densification

Glass microspheres before and after sintering by heating to allow viscous flow

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Coarsening mechanisms
• These mechanisms generally lead to coarsening, but not densification…why?
• Evaporation-condensation
• Surface diffusion
• Volume diffusion from the particle surface to the neck

32
Coarsening mechanisms
• These mechanisms generally lead to coarsening, but not densification
• Evaporation-condensation
• Surface diffusion
• Volume diffusion from the particle surface to the neck

• Without transfer of material from the region between the particles there is no way for the
particle centres to move closer together
• Will lead to change in pore shape, neck size, and increased strength of the part
• Smaller particles will tend to evaporate and condense on larger particle surfaces

33
Densification
• For densification, the atoms or ions must transfer from the interface between the particles to a
region of high vacancy concentration (i.e. neck or pore) via
• Lattice diffusion: from the grain boundary to the neck through the bulk of the grain
• Grain boundary diffusion: along the grain boundary to the neck

34
Kinetics of solid-state sintering
• Why does a powder compact densify rather than
coarsen?
• The relative rates of the different processes will
determine which, e.g. if surface diffusion is faster
than bulk diffusion a material will tend to
coarsen.
• However, many factors complicate the process
in practice, including:
• particle size and packing
• Atmosphere
• degree of agglomeration
• Temperature
• impurities Sintering of as-received vs deagglomerated yttria-
stabilised zirconia

35
Factors affecting solid-state
sintering
1. Temperature – increased temperature greatly increases diffusion and therefore sintering rate. Bulk
diffusion usually requires more energy than surface or GB diffusion, so higher temperature usually
enhances bulk diffusion and therefore densification.
2. Green density – higher green density leaves less pore volume to be eliminated, often leading to
higher final density.
3. Uniformity of green microstructure – variations such as agglomerates can lead to density
variations after pressing, which in turn affect sintered density.
4. Atmosphere – The atmosphere can alter the diffusion rate of some species and therefore affect
the dominant diffusion mechanism (remember Fe 2O3 - HCl?). The gas present in pores will also
affect their elimination based on its ability to dissolve into the solid.
5. Impurities – may affect sintering through many different mechanisms such as liquid formation,
altering diffusion rates or dominant mechanisms
6. Particle size distribution – small particle size increases surface area and driving force for
densification. Narrow size distributions reduce the likelihood of abnormal grain growth.

36
Grain growth
• Final stage of sintering involves grain growth
• Smaller grains eliminated as larger grains grow
• Micrographs clearly show decreasing grain
boundary area (therefore decreasing energy)

• Growth is dependent on grain boundary

movement

2D grain growth simulation: (a) to (d) CsI grain structure hot pressed at 103
https://www.youtube.com/watch?v=J_2FdkRqmCA MPa and 100°C for 5, 20, 60, 120 minutes. (e), (f)
fracture surface of (a) and (d).
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Grain boundary movement
• Grain boundary motion driven by the
curvature of different grains
• Equilibrium angle in this case must be 120°
(assuming equal surface energies on all GB’s)
• Grains with less than 6 sides will shrink due to
more acute angles (average angle = 360 / no.
of sides)
• Consider figure (b), the red atoms on the
convex side can become more tightly bound
(i.e. lower potential energy) by jumping the
grain boundary to join the other grain

38
 Grain boundary movement
• Must also remember that different crystal faces have different surface energies,
which also drives movement even of flat faces.
• Remember relating crystal morphology and structure?

Snowflake
Salt (Sodium chloride)

39
Microstructure and GB movement
• In reality GB’s are complicated by pores, impurities, second
phases that affect their movement, e.g.
• Solute drag – Solutes tend to accumulate at GB’s, and if the rate of
diffusion of the solute is low, the movement of the GB will be
slowed.
• Larger inclusion / second phases or higher concentrations of them
at the grain boundaries will move more slowly
• Boundary phase – in some cases a thin boundary phase forms
(remember GB glass in Si3N4?) that inhibit diffusion of atoms across
the GB (and therefore motion of the GB).
Grain-boundary glass in Si3N4
with Yb2O3
Y.-M. Chiang, D. Birnie, and W. D. Kingery. Physical
Ceramics:
Principles for Ceramic Science and Engineering.
Wiley, New
York, 1997.

40
Abnormal grain growth (AGG)
• A small number of grains grow to orders of magnitude
larger than the average
• Pores may become trapped in the large grains, inhibiting
densification
• Believed to be associated with formation of small
amounts of liquid during sintering

Normal vs abnormal grain

growth in Ti3SiC2

41
 Sintering 3
MEEN40080: Technical Ceramics
Kevin Roche BE, PhD
School of Mechanical and Materials Engineering
University College Dublin

42
This section

• Requirements for liquid-phase sintering

• Wetting
• Capillary forces
• Stages of liquid-phase sintering
• Particle rearrangement
• Solution-reprecipitation
• Skeleton sintering

Also refer to Fundamentals of Ceramics Chapter

10:
http://library.ucd.ie/iii/encore/record/C__Rb2551404 43
Liquid-phase sintering
• Formation of a liquid phase through either:
• 1. Lower melting point of second phase
• 2. Formation of a low melting-point phase
• Requirements:
• The liquid must wet the solid phase forming a liquid film covering the solid
• The solid must be soluble in the liquid
• Fast diffusion through the liquid phase of the species constituting the solid phase for
rapid sintering

44
Wetting
• Wetting – spreading of liquid across a solid surface
• displacement of solid/vapour or solid/solid interface by solid/liquid interface
• Similar equilibrium considerations to those discussed for solid-state sintering
• Liquid/grain boundary equilibrium:
• Liquid/solid/vapour equilibrium:
• High , low or promote wetting

45
Capillary forces
• Capillary forces become important in thin tubes
or similar closely spaced surfaces, such as in
pores and between grains
• Thinner spaces = greater effect
• Diagram shows a simple capillary tube in a
wetting or non-wetting liquid
• If the liquid is wetting, surface energy forces
draw the liquid upwards until equilibrium with
the downwards force of gravity is reached
• h inversely proportional to r
• In liquid-phase sintering this can lead to strong
forces to draw liquid into pores or between
grain boundaries, driven by
• Finer particles = greater capillary forces

46
Liquid between solid surfaces
• Consider a solid cylinder between two plates, heated to a liquid state
• If it wets the surfaces, the liquid is drawn out along the surfaces, but to maintain volume the
surfaces must move closer together
• Therefore a wetting liquid between particles creates a stress to draw the particles together
• Opposite if non-wetting

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Effect of liquid in sintering
• Sintering is much more rapid than solid state: full density in
as little as 15 minutes

• Typical systems
• WC-Co: WC particles (Tm=2870°C) in lower melting point Co
binder (Tm=1495°C)
• Si3N4-Al2O3-Y2O3 (Sialon): components react to form lower
melting point phase

Bubble raft ‘sintering’ video: https://www.youtube.com/watch? WC-Co microstructure

v=ah1Q6yqTdpA R. M. German. Fundamentals of
(Note this is simplified compared to real sintering sintering. In Schneider [24],
pages 260–269.
processes but still a great visualisation)

48
Stages of liquid-phase sintering
• Typical curve of liquid phase sintering (note
log time axis)

• Three regimes
• Particle rearrangement
• Solution-reprecipitation
• Skeleton sintering

49
Particle rearrangement
• Driven by imbalance in capillary forces due to:
• Particle size distribution
• Irregular particle shape
• Local density fluctuations
• Anisotropic material properties
• Rapid process, 100% may be achieved almost instantaneously

50
Solution-reprecipitation
• Capillary forces increase the chemical potential at contact points relative to other regions
• Solid dissolves at grain contacts and reprecipitates on uncompressed surfaces after diffusion
through the liquid, leading to flattening of the contact points
• Two possible rate-limiting steps
1. Diffusion rate of the material through the liquid (rate is orders of magnitude greater than in a solid)
2. Rate of interfacial reactions

• For small particles the process is controlled by step 2

• If rapid grain growth occurs then step 1 controls the process
• Small particles will tend to dissolve and reprecipitate on larger grains

51
Effect of small amounts of liquid
• Even small amounts of liquid can have a dramatic effect on grain growth (even in some nominally
solid-state sintering processes)
• Example shows the microstructure of TiB2/TiC sintered at temperatures where (a) no liquid forms,
and (b) a small amount of liquid is present.

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Skeleton sintering
• Once a rigid skeleton forms (continuously joined network of solid particles) solid state sintering
dominates and rates are greatly reduced

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