SINTERING OF CERAMICS

THEORY AND PRACTICE

Ender Suvacı
Anadolu University
Department of Materials Science and Engineering
26480 Eskisehir, Turkey

ANADOLU UNIVERSITY February 13, 2008

Element Six, Springs, South Africa
The four basic elements of materials science and engineering.
 Powder-Based Production of
Advanced Ceramics

Organic
Powder Powder Forming or
Synthesis Drying Binder Sintering
Dispersion Shaping
Removal

Polymers Dry Pressing Proof Test

Dispersants Pressure Filtration

Plasticizers Slip Casting

Mold release Tape Casting

Defoaming Injection Molding
agents
Extrusion
Types of Sintering
Typical microstructures
observed during (a) solid
state sintering (a-Al2O3)
and (b) liquid phase
sintering (98W-1Ni-1
Fe(wt.%))
Sintering,
• a heat treatment process

• a processing step to produce materials with controlled

microstructure and porosity, constantly

• involves material transport (i.e., diffusion)

• results in reduction in porosity and increase in mechanical

strength of the compacts.
 Driving Force And Basic Phenomena

Thermodynamic Perspective:
For sintering to occur, there must be a decrease in the free
energy of the system.
Both densification and coarsening result in reduction in free
energy of the system. Therefore, there are competitive
processes.
Schematic of (a) a system containing a phase a, a phase b
and an interface s and (b) atom density near the interface.

Young-Laplace Equation
DP=Pa - Pb =2g/r
 The curvature of the free surfaces results in
• chemical potential energy difference
• vapor pressure difference
• solubility difference
Kelvin-Thompson Equation

Driving Force:
The curvature of the free surfaces and when used, the
externally applied pressure
Kinetic Perspective:
Diffusion process should be high enough to
cause densification.

 Diffusion process is directly related with defect chemistry

of the material system.

 As Temperature increases, number of vacancies (i.e.,

point defects) increases exponentially.

 Dopants may also induce point defects.

 EQUILIBRIUM CONCENTRATION
OF POINT
• Equilibrium concentration variesDEFECTS
with temperature!

No. of defects Activation energy

ND =  -Q 
exp D 
N  kT 
No. of potential Temperature
defect sites. Boltzmann's constant
(1.38 x 10 -23 J/atom K)
(8.62 x 10 -5 eV/atom K)
Each lattice site
is a potential
vacancy site
 DIFFUSION AND TEMPERATURE
• Diffusivity increases with T

pre-exponential [m2/s]
activation energy
 Q  [J/mol],[eV/mol]
diffusivity D = Do exp - d 
 RT 
gas constant [8.31J/mol-K]

• Recall; vacancy concentration: NV = N exp(-QV/kT)

• QV is vacancy formation energy (larger this energy, smaller the

number of vacancies)

• Qd is the activation energy (larger this energy, smaller the

diffusivity and lower the probability of atomic diffusion)
 Variables Affecting Sinterability and Microstructure

Powder:
Variables related to
Shape, size, size distribution,
raw materials (material variables)
agglomeration, mixedness, etc.
Chemistry:
Composition, impurity, non-
stoichiometry, homogenity, etc.
Variables related to sintering
Temperature, time, pressure, atmosphere,
conditions (process Variables)
heating and cooling rate, etc.
 Development of
Polycrystalline Microstructures
 Interfacial Tension and Dihedral (Thermal Etching) Angle

Dihedral Angle

Wetting Angle
Distribution of a second phase with various dihedral angles in
a two dimensional microstructure.
Schematic of three-dimensional distribution of a second
phase with dihedral angle of (a) >600 and (b) >600.
Fracture surface of a W-Ni-Fe heavy alloy showing
distribution of a Ni-Fe-W matrix phase between W(Ni,Fe)
grains. 98W-1Ni-1Fe (wt.%) sample sintered at 14600C for 10
min. H2.
Solid State Sintering
Stages of Solid State Sintering
 Initial Stage Intermediate Stage

Near the End of the Initial Stage Final Stage

Lucalox alumina, after a) compaction, b) 1, c) 2.5, and d) 6 min. @1700°C
Material Transport Mechanisms
 Sintering Diagrams

Sintering diagram of an aggregate of pure silver spheres of 38 micron radius.

Effect of Sintering Variables on Sintering
 Aggregate Formation in Fine Particle Systems

Aggregate: A mass of interconnected particles bonded together by solid necks

of significant strength (e.g., sinter and chemical bonds)

Agglomerate: A mass of interconnected particles bonded together by weak

forces (e.g., Van Der Waals, electrostatic, liquids, polymers.
Aggregate/Agglomerate Effects on Sintering
Differential Shrinkage: The fact that the particle system is not ideally packed
means that differential shrinkage must occur. Additionally, differential
shrinkage as a result of agglomerates can adversely affect densification.
Lange and Metcalf (J. Am.Ceram. Soc. 66 398-406 (1983)) demonstrated that
if ragglomerate > rmatrix, then the matrix shrinks more than the agglomerate
resulting in a compressive stress around the agglomerate which is then
relieved by radial cracking.

if ragglomerate < rmatrix, then by similar arguments as above a

circumferential tensile hoop stress is generated around the agglomerate
which can be relieved by circumferential cracking.
Herring’s Scaling Law
‘Ideal’ Powder Characteristics for Advanced Ceramics

1. Particle size between 0.1 and 1.0 mm diameter

Upper size limit is established by thermodynamics of sintering
Lower size limit is set by need to avoid particle flocculation

2. Narrow particle size distribution

3. Equiaxed particle shape

Required to achieve most uniform packing and highest packing density
4. Dense particles
Minimum shrinkage requirement

5. No powder defects (e.g., agglomerates, aggregates)

They destroy the benefits of 1-4

6. Chemical purity and stoichiometry

 ANISOTROPIC SHRINKAGE IN
SINTERING OF ALUMINA CERAMICS
WITH ORIENTED PLATELETS*
Process Flow Chart Preparation of aqueus
alumina (45 vol.%) suspension

Three different compositions Ball Milling for 15 h

were prepared: samples
containing 0 , 10 and 20 Addition of Platelets
vol. % platelets
20mm
Addition of Organics
(6 vol. % PEG, 30 vol.% PVA)

Ball Milling for 15 h

Tape Casting (400 µm, 20 cm/sec)

Hexagonal alpha alumina Cutting and Lamination (75 MPa, 70°C, 5 min)
platelet particles (Elf-
Atochem)
Binder Removal and Sintering

Characterization (SEM, XRD and dilatometer)

Dilatometric Experiments
z

x
(Tape Casting Load = 10 g
Direction) x, y
y Saphire

Sample
Notation: Alumina
Saphire Substrate
T % pl- (x/y/z): T refers to volume z
fraction of platelets Sintering was performed at
x : tape casting direction 1550C for 1h.
y : transverse to the tape
casting direction
z : direction perpendicular to the
tape casting plane
Platelet-free a-Al2O3 samples exhibit isotropic
shrinkage.
1800 0,02 Temperature (°C)
1h 0 0 %-pl-x
1600
-0,02 0 %-pl-y
1400
(°C)

-0,04 0 %-pl-z
Temperature(°C)

1200 -0,06

Strain
Temperature

-0,08

Strain
1000
-0,1
800
-0,12
600 -0,14
-0,16
400
-0,18
200
-0,2
0 -0,22
0 5000 10000 15000 20000 25000 30000 35000
Time (s)
Time (s)

Shrinkage curves of 0 vol.% platelet containing a-Al2O3 system.

Addition of platelets results in retardation of sintering and
induces anisotropic shrinkage in a-Al2O3 samples.

1800 0,02 Temperature (°C)

0 10 %-pl-x
1600
-0,02 10 %-pl-y
1400
-0,04 10 %-pl-z
(°C)
Temperature (°C)

1200 1350°C -0,06 0 %-pl-x-y-z

Temperature

-0,08
1000

Strain
Strain
1530°C
-0,1
800
-0,12
600 -0,14
-0,16
400
-0,18
200
-0,2
0 -0,22
0 5000 10000 15000 20000 25000 30000 35000
Time (s)
Time (s)

Shrinkage curves of 10 vol.% platelet containing a-Al2O3 system.

 Microstructures of (a) 0 and (b) 10 %-pl samples sintered at 1350°C.
Densities of 0 and 10%-pl samples were 90% and 76% TD, respectively.
(a) 10 µm 2 µm

(b) 10 µm 2 µm
 Simulation of Stresses in Matrix Exerted by
Rigid Inclusions

z
tensile

compression

FEMLab Software was used for simulation

Shrinkage is constrained in x and y directions due to formation
of a dense a-Al2O3 network by dense matrix areas and
platelets in these directions. (15300C)

10 µm 2 µm

Microstructure of 10%-pl sample sintered at 1530°C. Density of the sample is

87% TD.
A higher retardation in shrinkage is observed in z-
direction for 20%-pl sample.
1800 0,02 Temperature (°C)
0 20 %-pl-x
1600
1350°C -0,02 20 %-pl-y
1400
1550°C -0,04
(°C)

20 %-pl-z
Temperature (°C)

1200 11 min -0,06

Temperature

-0,08

Strain
1000

Strain
-0,1
800
-0,12
600 -0,14
-0,16
400
-0,18
200
-0,2
0 -0,22
0 5000 10000 15000 20000 25000 30000 35000
Time (s)
Time (s)
Shrinkage curves of 20 vol.% platelet containing a-Al2O3 system.
 Significant degree of decohesion is observed between
platelets and matrix grains in 20%-pl samples.

10µm 2 µm

Microstructure of 20%-pl sample sintered at 1350°C. Density of the sample is

66% TD.
Dense a-Al2O3 network, which causes constraint effect in x
and y directions, forms at a lower density value in 20%-pl
samples than that in 10%-pl sample.
10 mm

Microstructure of 20%-pl sample sintered at 1550°C for 11 minutes.

Density of the sample was 78 % of theoretical density.
Addition of rigid inclusions such as platelets into fine
powder matrix results in constrained sintering and usually
anisotropic shrinkage.

The degree of this effect changes as a function of;

• Effect of platelets on packing of matrix grains

• Stress distribution around platelets
• A dense alumina network formation ability
through the sample.
Grain Growth
 Types of Grain Growth

• Normal Grain Growth

• Abnormal Grain Growth,

Exaggerated or Discontinuous Grain Growth,

• Anisotropic Grain Growth

 Normal and abnormal grain growth
normal grain growth - obeying Ostwald’s ripening law
- uniform grain size distribution

ZnO sometimes for ‘no reason’

CaTiO3 these rules break down
BaTiO3
&

we get unusual
exaggerated grain growth microstructures
- we observe few LARGE grains
- bimodal grain size distribution
- X ray shows a ‘pure’ phase

anisotropic & exaggerated grain growth

- ANISOTROPIC grains even in cubic materials!

- X ray analysis again shows a ‘pure’ phase
Grain Growth  Grain Boundary Velocity
 Grain Boundary Velocity

V=M.F
where
V= Grain Boundary Velocity,
M= Grain Boundary Mobility,
F= Driving force for Grain Boundary Migration
Driving force for grain boundary migration
versus grain boundary velocity
 The Zener Effect:
Dragging of grain boundary movement by
second-phase particles.
Grain Growth Kinetics

where,

k: constant
R: gas constant
T: Temperature
Q: activation energy for the growth
G: Grain size after time t
G0: Initial grain size
Liquid Phase Sintering
General Requirements for Liquid Phase Sintering

• An appreciable amount of liquid must be present

• Solubility of solid in a liquid

• Wetting of the solid by the liquid

Stages of Liquid Phase Sintering

Final pore
removal