Processing of ceramics

• Raw Materials/Batch preparation

• Forming/Consolidation

• Firing/Sintering

• Finishing (Surface finish, dimensional accuracy etc)

• Characterization
Attrition Milling
• Cylinder containing balls, agitated by a series of stirring-arms mounted to an
axial shaft

• Quicker than ball mill

• More efficient at achieving fine particle size

• Results in less contamination

Turbo Mill
• Changed version of an attrition mill

• Rotating cylindrical cage of vertical bars, surrounded by a stationary cylindrical

cage of vertical bars

• Materials to be grinded mixed with water or other fluid, plus sand-sized

grinding media

• Zirconia, Alumina & Silica grinded to submicron size in a few hours, compared
to 30h for vibratory milling & much longer time for ball milling

• Primary Problems

Contamination
Difficulty in separating media from the powder
Vibratory Mill
• Energy provided via vibration rather than tumbling & mechanical stirring

• Powder placed in stationary chamber + grinding media & a liquid. Vibrations

transmitted through the chamber & into the media and powder, when mill
turned on

• Two type of movement occurs:

Cascading or mixing action (of the contents)
Local impact & shear fracturing (of the powders)

• Also used for deburring (smoothing edges/ridges) & cleaning of metal parts
Fluid Energy Mill

• Size reduction achieved via particle-particle impact in a high-velocity fluid

• Compressed air, nitrogen, carbon dioxide, superheated steam, water or any

other gas or liquid compatible with the specific equipment design can be used

• Powder added to a fluid, accelerated to sonic or near-sonic velocity through jets

leading into the grinding chamber. Chamber designed so that particle-particle
impact maximized & particle-wall impact minimized
CHEMICAL SIZING
Precipitation

• Widely used method for both particle sizing & purifying of oxide ceramics

• Production of Alumina from Bauxite via Bayer Process relies on controlled

precipitation
Alumina uses: High temperature cement, sandblast nozzles, armor, crucibles, etc
Freeze Drying

• Mixture of soluble salts with desired ratio of metal ions, dissolved in distilled
water

• Droplets 0.1-0.5 mm dia rapidly frozen - very small ice crystals nucleate

• Sublimation carried out in vacuum – avoid liquid phase formation (prevents

segregation)

• Powders calcined (heat-treated). Decomposition of crystallized salt occurs,

gets converted to fine crystallites of the desired oxide or compound
Limitations
• Not all compositions achievable why?

• Soluble salts containing the required metal salts not available

• Some salt combinations form a precipitate, due to reaction

• Ex: Lead Zirconate Titanate – Salt not available

• Ex: Barium Acetate + Ferrous Sulfate results in precipitation of insoluble BaSO4

Sol-Gel Method
• Form Sol (by forming stable dispersion of particles less than 0.1 m dia in a
liquid)

• Form Gel (by inducing polymer-like 3D bonding): Change

concentration/evaporation, aging or addition of electrolyte

• Evaporate remaining liquid

• Increase temperature to convert dehydrated gel to ceramic composition

Metal Alkoxide M(OR)n

M is Metal ion of valence n
and R is an Alkyl group
CxH2x+1
Spray Roasting
• Fine droplets of precursors solution in water or other fluid sprayed into a
heated chamber with appropriated chosen Temp for chemical reaction to
occur

• Pyro-hydrolysis: Typically metal chloride in water sprayed into heated

ceramic-lined chamber

• Powder of 0.2-0.4 m in dia results, agglomerated in spheres of 100-200

m dia
Decomposition
• Carbonates, Nitrates, Sulfates, Oxalates & other compounds having oxygen ions
used in ceramic production

• Calcining or sintering (high temperature) yields the desired oxide

• Ex: MgCO3 decomposes to MgO

• Nonoxide raw materials used for reasons such as purity, particle size, availability,
or requirements to make soluble compositions etc
Hydrothermal
• Involves crystallization of a composition in hot, pressurized water (temperature
range from 100-350 C at pressure up to 15 Mpa)

• Feedstock can be oxides, hydroxides, salts, gels, organics, acids, bases

Plasma
Powder can be synthesized in high-temperature plasma (ionized gas).
Types:
• DC Arc Jet System (Contamination risk)
• Rf induction System (little contamination, but efficiency lower than DC arc jet)

Both processes used to produce SiC particles using SiCl4, CH4 & H2 as the gaseous
precursors. Si3N4 has also been synthesized by this technique

Laser
SiC & Si3N4 both can be produced by using laser energy
Rotary Kiln
Cylindrical rotating furnace, provide continuous mixing & minimize bonding of
adjacent particles

Fluidized bed
Porous plate supports powders. High pressure gas lifts & allows the complete bed
of powder to percolate. High-temperature fluidized bed used for calcining,
synthesis, & deposition of coatings by vapor reactions

Self-Propagating Combustion
• Self-propagating high temperature synthesis (SHS) forms ceramics and
intermetallic compositions through exothermic reactions

• Mg, Al, Ti are highly reactive when heated to moderate temperature. They
ignite and burn in air at very high temperatures to form oxides. In an inert
environment in contact with carbon or boron, they can react exothermically to
produce carbides and borides. Takes less than a second.
Calcining
• High temperature heat-treatment

• Dehydration, decomposition, reaction & coarsening occurs

• Pre-reaction of powders carried out (prior to compaction) to avoid buildup of

pressure that may crack powder compact
 Batch Determination

BaCO3+TiO2 BaTiO3 + CO2

137.33+12.011+3(15.999) 47.88+2(15.999) 137.33+47.88+3(15.999) 12.011+ 2(15.999)
197.338 79.878 233.207 44.009

For a 20g batch you would need (197.338/233.207)20= 16.9238 g of BaCO 3 and 6.85039 g of TiO2
Liquid Mix Process/Pechini
Process/Amorphous Citrate Process
Starts with a homogeneous solution containing the desired cations,
which uses additives and evaporation to convert the homogeneous
liquid to a rigid cross-linked polymer, and which utilize heat to
convert the polymer into a homogeneous oxide powder.

Following Steps are used to achieve a powder

Spray Roasting
Hydrothermal
Involves crystallization of a composition in hot, pressurized water. Typical
temperature range from 100-350 C at pressure up to 15 Mpa
Feedstock can be oxides, hydroxides, salts, gels, organics, acids, bases

Plasma
It’s a high temperature, ionized gas
Powder can be synthesized in high-temperature plasma environment
Two types
DC Arc Jet System (Risk of contamination)
Rf induction System (No contamination, however efficiency is lower than DC arc
jet)

Both process has been used to produce SiC particles using SiCl 4, CH4 and H2 as the
gaseous precursors. Si3N4 has also been synthesized by this technique

Laser
SiC & Si3N4 both can be produced by using laser energy
Calcining
Refers to high temperature heat treatment: Dehydration,
decomposition, reaction & coarsening
Rotary Kiln
Cylindrical furnace that rotates, the later helps free flow of the powder, provide
continuous mixing and minimize bonding of adjacent particles

Fluidized bed
A porous plate supports the powder in an enclosure. High pressure of gas
through the pores lifts the particles off the surface and allow the complete bed
of powder to percolate. A high-temperature fluidized bed can be used for
calcining, synthesis, and deposition of coatings by vapor reactions

Self-Propagating Combustion
Self-propagating high temperature synthesis (SHS) forms ceramics and
intermetallic compositions through exothermic reactions. Mg, Al, Ti are highly
reactive when heated to moderate temperature. They ignite and burn in air at
very high temperatures to form oxides. In an inert environment in contact with
carbon or boron, they can react exothermically to produce carbides and borides.
Takes less than a second.
Gas Condensation
Can produce ultra-fine nanometer sized powders – Brings
densification temperature down by 400-600°C

Nanophase material formed using these powders have

unique properties. For instance TiO2 with a grain size of
12nm has shown substantial ductile behavior at RT

The apparatus consists of an ultra high vacuum

system, resistively heated evaporation sources, a
liquid nitrogen-filled condensation tube, and a
scraper to remove condensed powder from the
surface of the tube.
PRECONSOLIDATION
This is a special treatment or processing prior to compaction.
Preconsolidation minimizes severe fabrication flaws that may occur
in the final processing steps.

Ex:
Non-free-flowing powder can result in poor distribution of powder
in the pressing die and distortion or density variation in the final
part

Improper viscosity control of casting slurry can result in incomplete

fill of the mold or a variety of other defects during slip casting

Inadequate de-airing of either slurry or an injection molding mix

can result in a strength limiting void in the final slip-cast or
injection-molded part
Spray Drying
Commonly used to achieve a uniform free-flowing
powder

It consists of a conical chamber that has an inlet for

hot air. Powder suspended in a slurry with
appropriate additives are fed-in through an
atomizer and is swirled around by the hot air
circulating in the chamber.

Some powder may react with water. Alcohol or

other nonaqueous fluid and an inert gas can be
used
GRANULATION
This is another approach to achieve better flow
properties of a powder

A damp or plastic mix is prepared instead of a

slurry for instance a Muller mixer may be used. For
lab scale, Mortar and Pestle or even hands can be
used.

The powder is screened and the agglomerates are

usually harder and more dense. Do not flow
readily but tend to pack to a lower volume
Dolomite ( /ˈdɒləmaɪt/) is an anhydrous carbonate mineral
composed of calcium magnesium carbonate, ideally
CaMg(CO3)2

Cryolite (Na3AlF6, sodium hexafluoroaluminate)

Coal is a hard rock which can be burned as a solid fossil

fuel. It is mostly carbon but also contains hydrogen, sulphur,
oxygen and nitrogen. It is a sedimentary rock formed from
peat, by the pressure of rocks laid down later on top