Fabrication of ceramics

Fabrication of ceramics
The very specific character of ceramics high
temperature stability makes conventional fabrication
routes unsuitable for ceramic processing.

Most other ceramic products are manufactured

through powder processing.

Typical ceramic processing route:

powder synthesis
green component (compaction)
sintering
Stages involved in the conventional fabrication
 Chemical synthesis methods
Capable of good control of composition and
homogeneous (atomic scale) mixing.
Lead to lower level of contamination.

The various methods are:

Chemical vapor deposition (CVD)
Inert gas condensation
Precipitation/co-precipitation
Pyrolysis
sol-gel
 Illustration showing the movement of balls and
powders in a Ball Mill
Major Variables:
Powder to ball ratio
(1:4)
Milling ball type (WC
or Al2O3 or ZrO2 or
agate balls)
Milling Speed
Milling Duration
Milling environment
(inert gas flow to
prevent oxidation of
metallic powders)
Milling medium (wet-
toluene/acetone vs.
dry)

S.-J. L. Kang, Sintering: densification, grain growth and microstructure, Elsevier, London (2005).
 High energy ball milling (HEBM)
High energy
collision
High shearing
action between
hard balls and
powders

Lead to particle size reduction by comminution as well

as grain size reduction by internal energy generation.
High yield and simple in procedure.
Gained lot of applicability industrially as well as in
research laboratories.
 Limitations of HEBM
Result in contamination and
broad particle size
distribution.

Lower limit below which

refinement not possible. Change of crystallite size of
Lower limit Al2O3 with milling time.
corresponding to the
scale at which
ceramics become Scr. Mater., 2001, 44, 293297
nearly perfect.
 Typical properties of nanocrystalline powders
Enhanced tendency to form agglomerates.
Presence of surface contaminants
SiC

J. Mat. Proc. Tech. 9293 (1999) 77

Centrifugation, ultrasonication, ball milling employed to break

agglomerates
Handling in vacuum/inert gas conditions and special chemical treatments
recommended
 Problems associated with nanosized powders

Interparticle/intercrystallite porosity with small sizes and interagglomerate porosity with

larger sizes.
Y-M Chiang, D. P. Birnie, W.D. Kingery. Physical Ceramics; John Wiley & Sons, Hoboken,
New Jersey, USA(1997)
 Synthesis of ZrO2 powders
Quality can be controlled by
ultrafine particle size
a narrow size distribution
Amount and distribution of stabilizing oxides
(ytrria, calcia etc.)
Low impurity content
 ZrO2 Powder processing routes
Co-precipitation route:
Ytrria doped ZrO2 powders are obtained by ammonia
leaching of ZrOCl2 and YCl3/Y(NO3)3solution.
Plasma coating route:
Plasma decomposition of ZrCl4 to ZrO2 and co-milling
with yttria
Suspension drying method:
Y2O3 dissolved in HNO3 is mixed with monoclinic
zirconia powders and subsequently milled with Y-TZP
balls and calcined at 800C for 1 h in air to obtain yttria-
coated zirconia powders
 TiB2 powders
Titanium diboride powders can be prepared by

Direct reaction of titanium or its oxides or hydroxides

with boron over 1000C

Carbothermal reduction of titanium oxide ad boron

oxide

Hydrogen reduction of born halides in the presence of

titanium or titanium halides
 TiB2 powders
Borothermic reduction:
Large scale production
TiO2 + B4C+ 3C 2TiB2 +4CO

1 m
 TiB2 powders
Submicron-sized powders by mechanical alloying
of elemental Ti and B powders

Nano-size TiB2 by solution phase reaction of

NaBH4 and TiCl4, followed by annealing at 900-
1000C
Nanocrystalline TiB2 powders
Hydroxyapatite powders
 COMPACTION
Powders pressed into the desired shape and size
using a hydraulic or mechanical press to obtain
the GREEN COMPACT

Compaction without heating the powders: Cold

Pressing

High temperature compaction also possible

 Cod pressing
Compacting powders in steel die with applied uniaxial
pressure

Involves enhancement of packing of loose powders by

keeping in dies or punches and applying pressure to reach
green density

Rearrangement of powders occurs followed by mechanical

deformation

CP is essential to achieve controlled porosity as required for

filters, for brake pads, for retaining lubrication in service etc.
Conventional method of compaction: (1) Filling die cavity with powder by
automatic feeding system, (2) initial and (3) final positions of upper/lower
punches and (4) ejection of part

Problem with CP: variation in apparent density across the thickness

 Cold isostatic pressing (CIP)
Ceramic powder is sealed in a flexible bag and
submerged in a fluid and pressure is applied in all
directions

Uniform density can be achieved because of hydrostatic

pressure

Wet-bag CIP
Dry-bag CIP
 Cold isostatic pressing (CIP)
Wet-bag CIP process:

Ceramic powder filled in a rubber mold, and immersed in a fluid for

compaction

Isostatic pressure is achieved via transfer from pressurizing the

fluid, which then passes on to rubber mold
Dry-bag CIP process:

Only radial pressure (along the horizontal direction) applied between the
flexible mold and rigid shell, while the bag can rest on its top or bottom
surface

This is required for obtaining a quality surface finish and to handle

complicate parts
 Cold Isostaitc Pressing of Ceramic Powders

The pressure is around 300 MPa and it is carried out either in water or Oil.

CIP Is used to obtain desired shaped green body without density gradient.
 Sintering

Definition:
process of firing and
Sintering refers to the
consolidation of powders at T> 0.5Tm, where
diffusional mass transport leads to the
formation of a dense body.
 Batch sintering of large number of compacts

M.P. Groover; Fundamentals of Modern Manufacturing: Materials, Processes and Systems.

John Wiley and Sons Inc., Hoboken, NJ, 2010.
Sintering powder touches forms neck & gradually
neck thickens
add processing aids to help form neck
little or no plastic deformation

Adapted from Fig. 13.16, Callister 7e.

Sintering: useful for both clay and nonclay compositions.

15m

Aluminum oxide powder:

sintered at 1700C Adapted from Fig. 13.17, Callister 7e.
(Fig. 13.17 is from W.D. Kingery, H.K.
for 6 minutes. Bowen, and D.R. Uhlmann, Introduction
to Ceramics, 2nd ed., John Wiley and
Sons, Inc., 1976, p. 483.)
Advanced Sintering techniques
 Sintering
Following criteria must be met before sintering can
occur:

A mechanism for material transport must be

present
A source of energy to activate and sustain this
material transport must be present
 Stages of Sintering
First stage:
Rearrangement
Neck formation
Intermediate stage
Neck growth
High shrinkage
Pore phase continuous
Final stage
Much grain growth
Discontinuous pore phase
Pores elimination
 Changes in Initial stage of sintering

(a) Starting particles

(b) rearrangement

(c) neck formation

 Changes in Intermediate stage of sintering

(a)Neck growth
and volume
shrinkage
(b)Lengthening of
grain boundaries

(c)Continued neck growth and grain

boundary lengthening, volume
shrinkage and grain growth
 Changes in Final stage of sintering

(a)Grain growth
with discontinuous
pore phase

(b) Grain growth with

porosity reduction

(c) Grain growth with porosity

elimination
 Thermodynamics in Sintering

Sintering: a transformation process of a porous powder

compact to a dense solid

All solid/ vapor interfaces replaced by solid /solid interfaces

The driving force of sintering process: reduction of

surface energy of the particles caused by decreasing
their vapour-solid interfaces.
 Two possible paths by which a collection of particle can
respond to a heating cycle during sintering

a) Densification followed by grain growth. b) Coarsening where the

In this case, shrinkage of compact has to occur large grain grow at the
expense of smaller ones
 Basic phenomena occurring during sintering
The driving force of sintering process :reduction of surface energy
of the particles caused by decreasing their vapour-solid interfaces.

d(A) = Ad + dA < 0

= Specific surface energy

A= Total surface area

S.-J. L. Kang, Sintering: densification, grain growth and microstructure, Elsevier, London (2005).
 Sintering
d(A) = Ad + dA < 0

Typically S/S or S/V surface area is replaced by only S/S during

the initial stages of sintering- (A d) dominates

During final stages of sintering grain coarsening occurs (

dA) dominates

Ideally, sintering should lead to densification into the most close

packed arrangement of a hexagonal array of grains and should
evolve from a state of loose-packed spherical powders
 Sintering
Sintering process is associated with dynamic changes in
pore size and shape.
An interconnected pore channel is developed during the
intermediate stage of sintering

Once the shrinkage of these pores takes place to

significant extent (resulting in an increase in relative density
by ~30%), the final stage of sintering starts.

Isolated pores can now be removed by lattice diffusion

alone.
Pore size/shape during conventional sintering
 Two particle model for initial stage of sintering without
shrinkage and with shrinkage

x, r and a are neck dimension, neck radius of curvature and particle size,
respectively
S.-J. L. Kang, Sintering: densification, grain growth and microstructure, Elsevier, London (2005).
Two-particle model made of glass spheres (3 mm diameter)
sintered at 1000C.

x and r are, respectively, the radius of the neck and the sphere.
 Contact between two spherical particles during
solid state sintering
Work done in expanding a sphere of
agasisnt external constraint is eual to the dA= 8 r dr and dV= 4 r2 dr
increase ins surface energy 2
p
-p dV= dA

r
1 1
p
r1 r2

x = neck dimension

= neck radius

r= particle size
r >0 convex surface


Thompson-Frieundrich equation (TFE)

=RTlnC-RTlnCo=RTln(C/Co) = RTln(p/po)

G
i
ni

T,P,n ,n ,..n.
1 2
,n ...
i1 i1

dG VdP SdT

RTln(C/Co)= dA=(2Vm/r)

i.e. C=Co exp[(Vm/RT)(2/r)]

*
p=po exp[(Vm/RT) (2/r)]
 Sintering and Curvature effects: Two-Sphere model
showing the transport paths, the two curvatures and the
process leading to densification
 Atomic Mechanisms During Sintering
Evaporation and Condensation--- surface atoms
evaporation and sink to the neck due to the pressure difference

Surface diffusion ---surface atoms from one part to another

Volume diffusion- surface to neck area or from

GB to neck area

Grain boundary diffusion from GB area to

neck area

Viscous or creep flow- Liquid diffusion (Capillarity forces) or

plastic deformation
Sintering of three spheres: The diffusion paths from the GB
to neck surface and development of a pore
 Paths for mass transport: Three particle model
Q Rate limiting stage in solid state
sintering is the diffusion of slowest
diffusing ions along its fastest path

Q Ambipolar diffusion occurs in case of

ionic solids

Q Surface diffusion leads to particle

coarsening, instead of shrinkage

QOnly lattice diffusion (at final stage) and

GB diffusion (mostly in intermediate stage)
leads to densification.

1. Surface diffusion
2. Lattice diffusion from surface
3. Vapor transport
4. Boundary diffusion
5. Lattice diffusion from GB
6. Lattice diffusion from dislocations
Schematic illustration of three stages in solid state sintering
 SOLID STATE SINTERING (Herrings scaling Law)

x 192D b t
Dl = the lattice self-diffusion coefficient for the rate
6 limiting diffusing species

Db = boundary self-diffusion coefficient for the

r KT r
4
rate limiting diffusing species

= boundary thickness

80Dl
5 K = Boltzmann constant
x t
r 3 = vacancy volume
r KT x = neck dimension

t = time of sintering
p
t(r2 ) (r2) T = sintering temperature during sintering

= surface energy
t(r1 ) (r1)
r = the particle size of the powders

- Particle Size dependence of sintering kinetics

 Variation of diffusion coefficients with temperature

Dl= lattice (or bulk)

diffusion coefficient

Db=boundary (or
interface) diffusion
coefficient

Ds=surface diffusion
coefficient

Y-M Chiang, D. P. Birnie, W.D. Kingery. Physical Ceramics; John Wiley & Sons,Hoboken, New Jersey, USA (1997)
Schematics of the microstructure of sintered multiphase
ceramics

(a) two phases microstructure

(b) three phases microstructure

 Analysis of grain growth in ceramics

V= Mb*2*F Db= bulk diffusivity of host atom

Or, V= Mb*2* *(3/g) = boundary layer thickness,

~0.5 nm
V= dg/dt =Mb* /g
= vacancy volume
g2 - go2 = 2Mbt,
Mb= Grain boundary mobility
Mb = Db /KT V= Grain boundary velocity

dg/dt = 2.Mb..(3/g) F= Driving force

= interfacial energy
 Grain growth in ceramics
Normal/Continuous Vs. Abnormal/discontinuous/exaggerated grain growth

Q The grains with 6 grain edges: Equiaxed grains without any curvature
Q The grains with < 6 sides or grain edges shrink due to curvature effect
Q The grains with > 6 sides would grow at the expense of finer grains
 Growth of the largest grain

Grain shape equilibrium and direction of motion of grain boundaries in two dimensional
sheet (the grains are cylindrical in this case).
Note that grains with six sides are stable, while those with less than six shrink and those
with more than six will grow.
Exaggerated grain in Al2O3
Pores being trapped within grain(closed pores)
GB/Pore interaction: the break-away process

Differences between pore velocity pore

velocity and grain boundary velocity
leads to pore detatchment.
 Pore movement and pore shape during grain growth

Q Pore morphology changes during grain boundary migration for pores

attached to grain boundary. The total elimination of porosity depends on
the location of pores, pore size as well as on densification-grain size
trajectory
Q The grains at triple junctions shrink and resultantly, pores coalesce
leading to decrease in number of pores and pore growth
Coalescence of three triple junctions due to grain shrinkage
and associated increase of materials in the pocket
 Grain size and pore size
Boundary control, Pore control
and Pore separation

Doping:
can shift the pore separation
diagonally upwards, so that
the entry in this region can be
largely avoided during
sintering.
can shift the boundary
between boundary control and
pore control to roght i.e. at
given grain size transition to
the pore region occur at the
larger pore size in doped
ceramic
 Grain size- density trajectories measured for Al2O3.

Note the effect of MgO addition is to lower the rate of grain growth
relative to density.
While being attached to GBs, dopants reduce the driving force for GB
mobility
 Grain size density map for Al2O3.

Doping of MgO raises pore separation region and lowers grain size trajectory
(dotted line), making it possible to sinter to complete density.
Experimental evidence for grain growth

a) 5min b) 20min

Atomic view of a curved

boundary.

c) 60min d) 120min Atoms will jump from right to

Evolution of microstructure of left, and the grain boundary will
CsCI (hot-pressed at 103 MPa at move in opposite direction.
100C )
 Prevention of pore separation
Use of appropriate type of dopant in the required
amount

Tailoring the sintering temp. and time so that grain

growth can be limited
 Assumptions of sintering theories
Monosized spheres in point contact---
In reality, mostly nonspherical powders with
wide size distribution;
Compaction repacks the particles , collapses
large pores and enlarges the particle contact
but may introduce new defects

Sinter under isothermall conditions

Major bonding between particles occurs prior to
attaining the maximum temperature