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MECHANICAL
ALLOYING
Process Variables of MA
Mechanism of MA
Introduction to Mechanical Alloying
Characterization and Applications

2
Introduction to Mechanical
Alloying (MA)
Alloying of difficult
to alloy metals
Amorphous
phases
Crystalline
phases
Nanometer
grain sizes
Extension of
solid solubility
Fine dispersion
of second phase
particles
Attributes
of MA

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Mechanical
Alloying
Milling of Mixture of powder
(metal or alloys / compounds)

Material transfer =>
Homogeneous alloy

Milling of uniform composition , i.e
pure metals, intermetallics, or
prealloyed powder

No material transfer for
Homogenization
Mechanical
Milling
Introduction to Mechanical
Alloying

5
No PCA, Oxide + Carbide dispersion
in Al
Graphite + Milling atmosphere control
(O
2
,Ar, N
2
) => Al + Al
4
C
3
+ Al
2
O
3



Milling of powder in Liquid Nitrogen.

Continuous flow of Liquid nitrogen
Or liquid nitrogen can be introduced
into the milling chamber


Reaction
Milling
Cryomilling
Introduction to Mechanical
Alloying
cont..

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Mechanical Alloying
MA is used to produce amorphous, nanocrystalline
and composite powders
Mixing of starting powders proportions
Loading powders into the mill
Mill to steady state

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Process
variables
in MA
Ball-to-powder
weight ratio
BPR
Type of mill
Milling time.
Milling energy
/speed
Grinding
medium
Extent of vial
filling
Process
Control
Agent
Process Variables

The planetary ball mills

Shaker mills
Attritors ball mills
Commercial mills




Types of Ball Mills

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The Planetary Ball mill
Clamping
Rotating
disk
Vial
Grinding
balls

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Planetary Ball Mill
cont..

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Mechanical Alloying (MA)
Horizontal section
Movement of
supporting disk
Centrifugal
force
R
o
t
a
t
i
o
n

o
f

v
i
a
l

cont..

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Retsch PM 200
Digital and
programmable

Planetary Ball Mill
WC
vials
cont..

Shaker mills

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With each swing of the vial, the
balls impact against the sample and
the end of the vial, both milling and
mixing the sample.
Because of the amplitude ( 5 cm)
and speed ( 1200 rpm) of the clamp
motion, the ball velocities are high
( 5 m/s), and consequently the force
of the ball's impact is unusually
great.
Vial is made up of hardened steel,
alumina, tungsten carbide, zirconia,
stainless steel.

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Attritors ball mills

Commercial mills

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PCA (lubricant or surfactant) is added to powder mixture
during milling to avoid the cold welding.
PCA can be liquid, solid or gas.
PCA are mostly organic compound, which acts as surface-
active agents.
Function of PCA:
PCA adsorbs on the particle surface and minimizes cold
welding.
lower the surface tension of solid material
Energy for size reduction:
E= .S

Process Control Agents (PCA)

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PCA Melting point (C) Boiling point (C)
Stearic acid
67-69

183-184

Ethyl acetate -84 76.5-77.5
Ethyl alcohol -130 78
Heptanes -91 98
Hexane -95 68-69
Methyl alcohol -98 64.6
Polyethylene glycol 59 205
Process Control Agents (PCA)
cont..

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PCAs are low melting and boiling point compounds

The majority of these compounds decompose during
milling

Process Control Agents (PCA)
cont..

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Hydrocarbons and carbohydrates introduce C, H and
oxygen into the powder particles that are uniformly
dispersed in the matrix.

The presence of air can also acts as a PCA and
prevents welding.

Milling of the powders at very low temperatures
(e.g., in liquid nitrogen) minimizes welding
Process Control Agents (PCA)
cont..

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PCA is used at a level of 1 to 5 wt% of the total powder
Amount of powder recovered increases with the increase of
quantity of PCA
PCA reduces the particle size by 2 to 3 order of magnitude.
Al powder milled for 5 hr
500m with 1 wt % stearic acid
10 m with 3 wt % stearic acid
Process Control Agents (PCA)
cont..

22

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Choice of PCA depends powder being milled and purity of
final product desired.
No universal PCA

Process Control Agents (PCA)
Amount of PCA
Cold
welding
Chemical
stability
Amount of
powder
cont..

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Milling Container
Milling container material can contaminate the
powder or alter the chemistry of milled powder
If material of container is different from that of
powder being milled, powder may be
contaminated.
If materials of container and powder are same,
chemistry may be altered e.g. milling of Cu-In-
Ga-Se in Cu container.

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Time is chosen to achieve a steady state between
fracturing and cold welding of powder particles to
facilitate alloying.
Milling Time

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Milling Energy
Faster the mill rotate, higher will be energy input
into the powder (E = mv
2
)

Limitations
Ball Pinning
Temperature
increase
wear of tools

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Impact energy depends on rotation direction of
vials and disks
Talc was milled in PM. Highest value
obtained was 15 kJ/s.kg in same direction
In counter direction, it was observed 80 kJ/s.kg
Ratio of rotation speed and revolution speed
Milling Energy
cont..

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Milling Energy
Milling Intensity:
I = BPR V
max
f
Where BPR= M
b
/ M
p

cont..

29
Also called charge ratio.
BPR has strong effect on the time required to
achieve a particular phase

10:1 BPR is commonly used.

Higher BPR can be obtained by increasing
number of balls or by increasing density of
balls.
Effect of Ball-to-Powder Weight Ratio

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Effect of Ball-to-Powder Weight Ratio
cont..

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Refinement of particle and grain sizes with milling time.
Rate of refinement increases with higher ball-to
powder weight ratios.

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The density of grinding medium must be high.
Stainless steel and WC are common grinding
medium
Use, if possible, same material of grinding
vessel and grinding medium to avoid
contamination
Size of grinding Balls
Final constitution of powder depends on size
of grinding balls.
Grinding Medium

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Grinding Medium
Highest collision energy can be obtained if
balls of different sizes are used.
If large differences in sizes of balls then
smaller balls will be destroyed by larger ones
Use combination of smaller and larger balls to
randomize the motion of balls

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If the quantity of the balls and the powder is very
small, then the production rate is very low.

If the quantity is large, then there is not enough space
for the balls to move around and so the energy of the
impact is less.

Generally about 50% or a little more of the vial space
is left empty.
Extent of vial filling

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During high-energy milling, the powder
particles are repeatedly flattened, fractured, and
rewelded.

Cold welding and fracturing depend on
deformation characteristics of powders
Mechanism of MA

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Mechanism of MA
Typical
starting
Powder
After
single
collision
Soft metal A
Dispersoid
Soft metal B
intermetallic
20m 20m 5m 5m
Ball-powder-ball collision

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Around 1000 particles with an aggregate weight
of 0.2 mg are trapped during each collision.
Ball-powder-ball collision

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(a)
(a)
Metal A
Intermetallic
Dispersoids
Metal B
0.5 micron
First stage of MA

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(b)
0.5 micron
Metal B
Metal A
Dispersoids
Dispersoids
interdiffusions
Intermetallic
Dispersoids
Metastable phase
Precipitate phase
Second
stage
of MA

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(c)
0.5 micron
dispersoid
Concentration of metal B
Concentration
of metal A
Remanent of
intermetallics
Equilibrium
precipitates
Third
stage
of MA

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Mechanical alloying involves powders with
very small sizes and these should be handled
with caution and care.
Because of the large surface area, they are
highly reactive and can be pyrophoric and can
cause health problems when inhaled.
Precautions should be taken not to open the
powder to atmosphere immediately after
milling since this can lead to oxidation of the
powders and in some situations they can even
catch fire.
Powder Handling

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