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Processing of ceramics
CERAMICS
Ceramics are found in electronic devices such as
computers, cell phones television etc. They have
many electrical properties which makes them act
as insulators, semiconductors, superconductors
which makes them suitable for the applications.
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Processing of ceramics
Sintering or
densification or
Forming firing
T≈
≈ 2Tm/3
powder compact or ceramic
“green”
Processing of ceramics
Starting powders
Milling
Mix with binder and other additives
Solvents:
Water
Organic solvents
(Tb= 100-140°C) Slurry/Slip/Paste Dry/Granulate
EtOH-MEK
Toluene-EtOH
Shape forming: Powder compaction/shaping:
Slip casting Powder compact: Dry pressing
Tape casting green Injection moulding
Extrusion
Dry
Binder burnout Binder burnout
Conventional
Dense
Hot-pressing Sintering
Sintering polycrystalline
Hot isostatic pressing body: ceramic
Spark plasma sintering
Finishing Machining and finishing
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Particle packing and granulation
“perfect” powder Maximum packing
In practice powders are
composed of particles with a
size distribution and often the
particle shape is not spherical.
Random packing of spheres with
a log-normal distribution ≈67%.
Particle packing and granulation
Particles with sharp edges
or formed by irregular
aggregates do not flow and
do not pack efficiently (r.d.
<50%). Granulation is
essential.
Angular shape of milled alumina
Sketch of an agglomerate
with uncontrolled shape
Granules can be obtained by forcing a
rigid ceramic paste through the mesh of
a sieve or, better, using a spray-drier
Schematic diagram of a spray-drier
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Powder consolidation and shaping
Dry powder, very
simple shapes. Uniform pressure gives
Die-wall friction uniform green density and
introduces density limits lamination. Used for
gradients which lead mass production of spark
to differential plugs and high-voltage
densification and insulators
distortions during
Uniaxial pressing sintering
Isostatic pressing
Traditional pottery industry
Viscous slip Plaster of and technical ceramics Up to 30% of organic
(50% solid) Paris mould (zirconia, Si3N4, SiC) additives (deflocculant,
binder and plasticizer).
Water or organic solvents.
Used for electronic
Water Moving substrates, multilayer
band ceramic capacitors and
Slip surplus
Tape casting actuators.
Slip casting
A ceramic paste containing
binders and lubricants is forced Ceramic powder + 40%
through the orifices of a die. thermoplastic, need
Components with uniform careful burnout.
section and high Complex shapes, high
length/diameter ratio, such as
Extrusion shrinkage (15-20%).
rods and tubes. Used also for Injection moulding
thick dielectric substrates.
Powder consolidation and shaping
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Powder consolidation and shaping
•Binder: gives the dry shape (green) sufficient strength for handling before sintering (starch, cellulose
ethers, polyvinyl alcohol, polymethacrylates, polyvinylbutyral).
•Deflocculant/dispersant: gives the suspension a high stability (electrostatic and electrosteric stabilization)
against sedimentation/flocculation required for casting (ammonium polyacrylate, citric acid).
•Plasticizer: gives flexibility to tapes and deformability to granules by lowering the Tg (glass transition
temperature) of binders (glicerine, butyl benzyl phthalate, poly(ethylen) glycol)
•Lubricant: decreases die-powder and granule-granule friction (salts of stearic acid)
Powder consolidation and shaping
The stages of dry pressing
Dry-bag isostatic pressing
Extrusion Double-gated injection moulding device
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Powder consolidation and shaping
Tape
Drying chamber
Casting head
Compact tape casting unit
Schematic of a doctor blade casting unit
IR lamp
Casting head
Non-continuously working laboratory casting unit
Continuously-working (20 cm/min)
industrial casting units
Sintering and grain growth
Sintering: removal of pores between particles accompanied by shrinkage (densification) and
grain growth.
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
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.
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Sintering and grain growth
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 (tetrakaidecahedra). This stage
continues until pores are closed (r.d. 90%).
tetrakaidecahedron
(d) Final stage sintering. Pores are slowly eliminated and major grain 6s+8h faces
growth can occur.
In hot-pressing and hot isostatic pressing an additional driving force is provided by the external
stress/pressure.
Initial stage Intermediate stage Final stage
Sintering and grain growth
Sintering mechanisms
Mechanism Source Sink Densification
1 Surface diff. Surface Neck No
2 Evaporation- Surface Neck No
condensation
Grain boundary
4 Volume diff. Grain Neck Yes
boundary
6 Grain boundary Grain Neck Yes
diffusion boundary
In ionic materials, the mobility of the slowest moving species dominates the
diffusion process and sintering rates. This explain the strong dependence of
sintering kinetics on nature and amount of uncontrolled impurities, dopants
and sintering aids. Grain boundary diffusion is the most important
densification mechanisms in many oxides.
Surface diffusion &
evaporation-condensation Positive curvature
Negative curvature
Volume and grain Nul curvature
boundary diffusion
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Liquid phase sintering
• Enough liquid phase must be present (1-5 vol.%).
• The liquid must wet the solid (contact angle θ<<90°).
• The solid must be partially soluble in the liquid. θ > 90°: nonwetting θ < 90°: wetting
•Driving forces are higher for small particles (stronger
capillary forces) with high surface energy and high
solubility θ = 0°: spreading
Particle rearrangement: the liquid spread on the
particles which rotate and slip. Significant
densification occurs, up to 70%, without modification
of particle and pore morphology.
Solution-precipitation:
(1) Ostwald ripening. Small particles dissolve in the
liquid and the material precipitates on bigger particles
because solubility depends on the radius of curvature.
(2) Dissolution occurs in the neck region because of
Laplacian compressive force and material redeposit
away of the neck region.
(3) Sharp corners dissolve and material precipitates
on regions of lower curvature.
Coalescence. When enough grain growth has
occurred, a solid skeleton is formed and the pores
becomes closed (at ≈90% re. dens.). Pore elimination
can proceed by solid-state diffusion.