Unit 2: Synthesis of Powders

The characteristics of the powder have a remarkable effect on

subsequent processing, such as consolidation of the powder into a
green body and firing to produce the desired microstructure.

A. DESIRABLE POWDER CHARACTERISTICS:

Traditional ceramics generally must meet less specific property

requirements than advanced ceramics. They can be chemically
inhomogeneous and can have complex microstructures.

The starting powders for an insulating porcelain can, typically, be a mixture

of clay (50 wt%), feldspar (25 wt%), and silica (25 wt%).

Generally, low cost powder preparation methods are used for traditional
ceramics.
 Advanced ceramics  specific property requirements, so control of
chemical composition, powder characteristics and microstructure.

(nanometer)

Particle size: If greater than > 1 m  generally precludes the use of colloidal
consolidation methods due to fast settling of the particles.

The rate at which the body densifies increases strongly with a decrease in particle
size. Note that if particle size is in the nanometer range  possibility of
agglomeration (but can be prevented)  bad for sintering (or densification)
Particle size distribution:
30
Monodisperse (or narrow)

Volume percent
20

Polydisperse (or wide)

10

0
0 1 2 3 4 5 6
Particle size, m

Wide particle size distribution may lead to higher packing density in the green
body, but causes difficulties in microstructural control during sintering  large
grains coarsen rapidly at the expense of the smaller grains, making the
attainment of high density with controlled grain size impossible  coarsening

Homogeneous packing of a narrow size distribution powder

generally allows greater control of the microstructure.
Spherical or equiaxial shape  beneficial for controlling the uniformity of the
packing in the green state.

Agglomeration  heterogeneous powder packing in the green body which, in

turn, leads to differential sintering (different regions of the body shrink at different
rates) → development of large pores and cracklike voids in the fired body.

Ideal situation  No agglomeration in the powder.

soft agglomerates  particles are held together by weak van der Waals
Forces  broken down relatively easily by mechanical methods (e.g., pressing or
milling) or by dispersion in a liquid.

hard agglomerates  particles are chemically bonded together by strong

bridges  not easily broken down and therefore must be avoided or removed from
the powder.
Surface impurities

i) A significant influence on the dispersion of the powder in a liquid

ii) Serious effects in sintering → Impurities may lead to the formation
of a small amount of liquid phase at the sintering temperature, which causes
selected growth of large individual grains  impossible to achieve a fine uniform
grain size in the microstructure.
Polymorphic Transformations

can also be a source of severe difficulties for microstructure control.

Common examples are:

ZrO2  cracking is a severe problem on cooling due to
tetragonal to monoclinic phase transformation

-Al2O3  the transformation to  phase results in rapid grain

growth and a severe retardation in the densification rate.
B. POWDER SYNTHESIS METHODS:

A variety of methods exist for the synthesis of ceramic powders but in general
there are two methods:

Mechanical methods: to prepare powders of traditional ceramics from naturally

occurring raw materials  mature area of ceramic processing. However, the
preparation of fine powders of some advanced ceramics by mechanical methods
involving milling at high speeds has received a fair amount of interest.

Chemical methods: to prepare powders of advanced ceramics from synthetic

materials or from naturally occurring raw materials after a considerable degree
of chemical refinement.

Mechanical step in some chemical methods  for the breakdown of

agglomerates and for the production of the desired physical characteristics such
as average particle size and particle size distribution.
C. POWDER PREPARATION BY MECHANICAL METHODS

C1. comminution

Mechanical
Big particles force
Small particles

Comminution involves operations such as crushing, grinding, and milling.

The most common way to achieve smaller (or fine) size reduction is by
milling:

* high-compression roller mills

* Jet mills (or fluid energy mills)
* Ball mills (tumbling, vibration, and agitation)

In the milling process, the particles experience mechanical stresses at

their contact points due to compression, impact, or shear with the mill
medium or with other particles.
The mechanical stresses lead to elastic and inelastic deformation
and, if the stress exceeds the ultimate strength of the particle, to
fracture of the particles.

The stress mechanisms and the range of particle sizes achieved

with different types of mills for the production of fine powders.
High-compression roller mills:

• The material is stressed between two rollers with a high contact pressure of
100-300 MPa.
• Difficult to break particles below ~10 m. Therefore, need other mills such as
ball mill to produce finer particles.
• Since only a small amount of material makes contact with the rolls, the wear
can be fairly low (e.g., much lower than in ball milling).
• No grinding media
Jet mills:
• Comminution occurs by particle–particle collisions in streams of high-speed gas
carrying the coarse particles (sometimes between the particles in the high speed
stream and a wall (fixed or movable) within the mill).
• The gas for the high-speed stream is usually compressed air, but inert gases such as
nitrogen or argon may be used to reduce oxidation of certain nonoxide materials
(e.g., Si).
• Multiple gas inlet nozzles to provide multiple collisions between the particles,
thereby enhancing the comminution process.
• No grinding media

Advantages  for the production of a powder with a narrow size distribution

for particle sizes down to 1 m. The particles do not come into contact with
the surfaces of the milling chamber, so contamination is not a problem.
http://www.sturtevantinc.com/products/overview/
Ball Mills:
Mills that incorporate grinding media (balls or rods)

• Comminution occurs by compression, impact, and shear (friction) between the

moving grinding media and the particles.
• ~ 10 m – submicron particle size by using balls (not rods)
• Suitable for wet or dry milling.
• Ball mills that run at low speeds  large balls are used because mechanical
energy supplied to the particle is in the form of potential energy. At high
speeds  small balls due to kinetic energy
• Size of grinding medium  Small grinding media are generally better than
large ones  number of contact points between the balls and the powder
increases  the rate of grinding will increase. However, the balls cannot be
too small since they must impart sufficient mechanical energy to the particles
to cause fracture.
• The rate of grinding also depends
on the particle size  The rate Figure 2.2
decreases with decreasing particle
size and, as the particles become
fairly fine (e.g., about 1 m to a few
micrometers)  practical grinding
limit.

Reasons  as particle size decreases;

i) tendency to agglomeration increases;
ii) probability for the occurrence of a comminution process decreases;
iii) the probability of forming a flaw in particle decreases i.e., the particle
becomes stronger.

Particle size decreases more by wet milling.

i. By using dispersant and
ii. Staged milling  as the particles get finer, they are transferred to another
mill operating with smaller balls.
Disadvantages  wear of the grinding medium  introduction of impurities to the
powder serious concern for advanced ceramics.

Solutions  to use balls with the same composition as the powder itself  but, ball
compositions are limited.
 to use a grinding medium that is chemically inert at the firing temperature
of the body (e.g., ZrO2 balls) or can be removed from the powder by
washing (e.g., steel balls). Porcelain balls or low-purity Al2O3 balls that
wear easily and introduce a fair amount of SiO2 into the powder  causes
problem during sintering.
 Tumbling ball mill (or ball mill)  slowly rotating horizontal cylinder that is
partly filled with grinding balls and the particles to be ground. The speed of
rotation influences both the trajectory of the balls and the mechanical energy
supplied to the powder.

critical speed of rotation  the speed required to just take the balls to the apex
of revolution where the centrifugal force just balances the force of gravity.
1/2
(g/R)
Critical speed (rpm ) =
2π
R: radius of the mill
g: acceleration due to gravity

apex

In practice, ball mills are operated at 75%

of the critical speed so that the balls do
not reach the top of the mill.

Figure 2.4.
 A: numerical constant that is specific to the mill being used and the
powder being milled
a: radius of the mill
: density of the balls
d: particle size of the powder
r: radius of the balls

As r decreases  rate increases, but the balls will not possess sufficient
energy to cause fracture of the particles if they are too small.

Objective  to have the balls fall onto the particles at the bottom of the mill
rather than onto the mill liner itself.
 For a mill operating at 75% of its critical speed;
Dry milling  balls: filling 50% of the mill volume
 powder: filling 25% of the mill volume

Wet milling  balls: filling 50% of the mill volume

 slurry (solid+liquid mixture): 40% of the mill volume with the solids
content of the slurry equal to 25–40%.

Laboratory practice is important for actual ratios

With proper solids loading (red), the grinding With too low a solids loading the media will
media (gray) will always have product to impact strike themselves resulting in ineffective
between the pieces of media. milling and increase media and mill wear.
http://www.pauloabbe.com/size-reduction/resources/ball-mill-loading-dry-milling
Wet ball milling advantages over dry milling:
i. higher energy utilization (by 10–20%).
ii. ability to produce a higher fraction of finer particles.
Disadvantages:
i. increased wear of the grinding media,
ii. the need for drying of the powder after milling,
iii. contamination of the powder by the adsorbed vehicle.

ZrO2 contamination in Al2O3 powders

* ZrO2 impurity
*
*

20 30 40 50 60 70

2, degrees
C. Duran, unpublished work, 2006
Vibratory ball mill or vibro-mills:
Consist of a drum, almost filled (90% of the mill volume) with grinding media (usually
cylindrical in shape) and the particles to be ground  vibrated fairly rapidly (10–20 Hz)
in 3D to produce an impact energy.
The 3D motion helps in the distribution of the charge of particles and, in the case of wet
milling, to minimize segregation of the particles in the slurry  faster and more energy
efficient than tumbling ball mills.

http://www.sweco.com/products/grinding-mills.aspx
Agitated (or attrition) ball mill: The milling chamber does not rotate; Instead, the stock
of particles and the grinding medium (small spheres of 0.2–10 mm and make up 60–
90% of the mill volume) are stirred rather vigorously with a stirrer rotating continuously.
aligned either vertically or horizontally
suitable for dry and wet milling,

Most agitated ball milling is also carried out continuously, with the slurry of particles to be
milled fed in at one end and the milled product removed at the other end. Considerable
heat is produced, cooling the milling chamber is required.

Horizontal mill
Advantages over tumbling and vibratory mills;

* Higher energy utilization more efficient grinding

* Higher solid content in the slurry possible

* Fine grinding media  improved rate of milling at shorter times 

less contamination (or impurity) of powders

* Contamination can be further reduced by lining the mill chamber with

a ceramic material or a plastic and by using ceramic stirrers and
grinding media
Vertical mill
C2: Mechanochemical Synthesis (mechanosynthesis, mechanical
driven synthesis, mechanical alloying, and high energy milling):

Milling  Change in physical and chemical properties of materials

• In comminution (or milling)  main idea to adjust particle size and particle size
distribution.
• Grinding enhances the chemical reactivity of powders  rupture of the bonds
during particle fracture  unsatisfactory valances and high surface area
increase favor reaction between mixed particles or between the particles and
their surroundings.
• This method has been investigated for the preparation of a variety of powders,
including oxides, carbides, nitrides, borides, and silicides.

Advantages: ease of preparation of powders such as silicides and carbides. For

example, most metal carbides are formed by the reaction between metals or metal
hydrides and carbon at high temperatures (as high as 2000C). Furthermore,
some carbides and silicides have a narrow compositional range that is difficult to
produce by other methods.

Disadvantages: incorporation of impurities from the mill and milling medium into
the powder.
Mechanism of mechanochemical synthesis is not clear. Possibilities;

• solid-state diffusion mechanism thermally activated processrequire lowering of

the activation energy and increase in temperature in the mill or some combination of
the two. Temperature increase in the mill is much lower than a true solid-state
mechanism.
• local melting of the particles due to exothermic reactions
• Self-propagating process due to exothermic reactions such as the formation of
molybdenum and titanium silicides from their elemental mixtures, the heat that is
liberated is often sufficient to sustain the reaction;

Mechanochemical
milling
Mo and Si powders MoSi2

A critical step for the formation reaction appears to be the generation of a

fine enough particle size so that the available surface and strain energy is
sufficient to make the reaction self-sustaining.
 Following an induction period (a), the reaction occurs quite abruptly (b). A small portion of
the elemental powders react during the milling process, the heat liberated by the reaction
ignites the unreacted portion until the bulk of the elemental powders is converted to the
product MoSi2.

Figure 2.6

The average particle sizes of the Mo and Si powders: 20 nm and 10 nm, respectively. High
surface energy due to high durface area, coupled with the stored strain energy, may provide
such a source of energy for sustaining the reaction to form MoSi2.
Synthesis of ZnO nanoparticles via the mechanochemical reaction ZnCl2 + Na2CO3
 ZnCO3 + 2NaCl and subsequent thermal decomposition of ZnCO3.
Scripta mater. 44 (2001) 1731–1734

TEM micrograph of the ZnO nanoparticles

XRD spectra of the ZnCl2 + Na2CO3 + obtained from a ZnCl2 + Na2CO3 + 8.6NaCl
8.6NaCl powder mixture before and after powder mixture.
heat treatment and subsequent washing