ELECTROCHEMICAL PROCESS

These methods are based on the electrolysis of molten

solutions of metals or fused salts.
The metals are electrically deposited on the cathode of
an electrolytic cell as a sponge or powder or at least in a
physical form in which it can be easily disintegrated
into a powder.
Advantages of the process:
The technique has a number of advantages, e.g.
The product is usually of a high commercial purity.
A considerable range of powder qualities can be
obtained by varying bath compositions.
Frequently the product has excellent pressing and
sintering properties.
The cost of the operation may in some cases be low.

Limitations:
Alloy powders cannot be produced.
The product of process is frequently in active
condition (presence of chemicals on powder particles)
which may cause difficulties in washing and drying it
(contamination/oxidation with atmospheric oxygen
may occur).
The cost of operation may be high in some cases.
Basic principle of the process and equipment used:
The equipment used is an electrolytic bath made of
steel, and lined from inside with rubber. Two
electrodes are inserted in the bath.
Cathode is made of lead while anode is made of the
same metal whose powder is being produced.

Principle:
The basic principle is the electrolysis process in which
decomposition of a molten salt/aqueous solution into its
ions is obtained by the passage of electric current. The
metallic ions are deposited at the cathode which can be
removed with a brush and collected at the bottom.
The electrolytic tanks have conical bottoms with a
valve. Suction pipes are connected to these bottoms and
powder is removed from the tank.
The efficiency of the tank/process depends on the
deposition rate.

Figure: Electrolytic Cell Operation for Deposition of

Powder --- Schematic.

Powder production at cathode is favored by:

high current density;
weak metal concentration;
addition of acids;
low temperature;
avoidance of agitation, and;
suppression of convection.
* Very fine powder can be obtained when the current flowing is so
strong in relation to the strength of the solution that hydrogen is strongly
evolved from the cathode.
Hydrogen evolution is encouraged by:
(i) increasing cell voltage;
(ii) diminishing the size of the cathode;
(iii) bringing the anode and cathode closer together;
(iv) increasing the temperature;
(v) weakening the strength of the metallic solution
(vi) adding acid

* When metal is deposited without evolution of

hydrogen, the deposit may be ductile and compact if the
current is just not great enough to cause hydrogen
formation, or very hard with large crystals using strong
solutions and large quantities of electricity, or sandy and
brittle with little cohesion using very small current.

DESIGN CONSIDERATIONS:
An outstanding characteristics of electrolytic powder
process is the large number of variables which either
have to be selected and fixed before plant is erected, or
which have to be controlled during operation. The most
important are;
(i) Electrolytes
(ii) Electrodes
(iii) Current
(iv) Flow of electrolyte
(v) Structural considerations
(vi) After treatment

Electrolytes:
The choice of the type of electrolyte will depend largely upon the
cost of the chemicals involved.
Electrolyte should not corrode the apparatus i.e., it should be of noncorrosive nature.
Concentration of the electrolyte should remain same with the passage
of time.
Cost:
Relatively pure salts of copper which are cheap and freely available
are uncommon, and therefore most copper powder production has
been derived from sulphate-sulphuric acid baths.
Some scientists are in favor of copper chloride bath because of better
cathode efficiency, lower cell voltage and less power consumption. It
is claimed that the chloride bath produces a more dendritic powder
with better pressing properties.

In the case of sulphate electroytes, the presence of a small amount of

chloride improves the anode current efficiency. Such additions may,
however, cause corrosion problems in the cells and deterioration of the
keeping qualities of the powder.
Iron powder ----- sulphate or chloride baths.
Having selected the type of bath, the exact composition must then be
chosen and thereafter maintained with considerable care
With copper sulphate/sulphuric acid electrolytes, it has been found that
cathode current efficiency improved as the copper content increased,
reaching a maximum of 96.4 % at 35 gm./liter, and decreased with
increasing acid, being 91.9 % at 25 gm./liter. The apparent density of
powder produced increased to a maximum of 0.663 gm./ml. at 8.6
amp./dm.2 and thereafter decreased, and similarly attained a maximum
of 0.42 gm./ml. at 100 125 gm./liter of H2SO4. The copper
concentration had a large effect on the apparent density which varied
from 0.42 gm./ml. at 5 gm./liter to 2.44 gm./ml. at 45 gm./liter.
Increasing the copper content substantially increased particle size of the
powder.

The electrolyte composition does not necessarily stay

constant during electrolysis. Variations are usually caused
mainly by differences in anodic and cathodic current
efficiencies.
In the case of copper, the concentration of metal in the
bath generally rises. Subsidiary effects are caused by
evaporation, by drag-out when the powder is removed, and
by the chemical solution of the electrodes when the current
is interrupted. Replace the electrolyte with fresh solution.
Control of temperature is also important. It was found
that as the temperature increases from 15 to 60 C, the
current efficiency increased from 66.8 to 91.4 % and the
apparent density from 0.451 gm./ml. to 0.746 gm./ml.

Electrodes:
The size, shape and disposition of electrodes may
vary widely.
The anode may be soluble or insoluble and may be placed
directly in the electrolyte or within a porous pot.
The anode may be of pure or impure metal, or in the form
of scrap supported in a basket. Unless, however, special
precautions are taken, impure anodes may cause operating
difficulties or at least contamination of the powder by the
formation of slimes.
It is unusual for the area of the anode to be larger or smaller
than that of the cathodes, for the purpose of balancing the
electrode efficiency.
For similar reasons, in order to improve the distribution of
powder deposit on the cathodes, it is recommended to use anodes
with rows of holes bored in them

In the case of cathodes, the choice may depend upon whether the deposit
is going to be stripped off or allowed to fall off in the form of a sponge
or powder, or weather it is intended to make a coherent brittle deposit.
In the former case, the choice is mainly a matter of minimizing
corrosion, especially at the liquid level, and facilitating clean stripping.
For copper ----- copper rod, Al sheets, Pb sheet.
For iron -------- Nb, Mo, Ta, W or Pb sheets
When the deposit is of a brittle nature, it may be removed either by
knocking it off or flexing the sheet cathode.
Sponge deposits may be removed using brushes.
Layers of graphite paint or oils may be employed to facilitate the
separation. Castor oil oxidized with 1-3 % perchloric acid applied by
pre-immersion has been used.

It is not unusual to make the deposition upon a cathode

starting sheet which is substantially crushed along with
the deposit. For example, iron gauze has been
recommended and used. This becomes embrittled
during the electrolysis and is readily crushed.
It has even been proposed to employ cold-pressed and
un-sintered or sintered cathode which easily
disintegrate.
Rotating electrodes

Current:
The choice of a specific operating current density will depend
mainly upon whether a coherent brittle or powdery spongy deposit is to
be made. In the former case the current density will be low, in the latter
it will be high.
In each case there may be an optimum density which gives the
highest current efficiency, but this may not necessarily be the same
density which produces the most suitable grade of powder.
Some workers have found that rising temperature increases the current
efficiency.
Apparent density of the product is unaffected by current density.
The frequency at which the current is interrupted has a most important
influence upon the particle size of the powder, and the longer the
intervals the larger the particle.
The greater the interval between current interruptions, the higher
is the apparent density.

Flow of Electrolyte:
In practice, convection and development of gas
bubbles cause a considerable flow of electrolyte over
the cathodes, and an important practical difficulty is to
maintain this reasonably constant. It would appear that
a certain minimum forced circulation would be helpful
in attaining this.
In an experiment it was found that stirring the
electrolyte coarsened the powder and increased the
apparent density.
As stirring is advantageous from the point of view of
evening out bath variables, but to some extent
disadvantageous in increasing the density and
therefore reducing the compressibility.

Structural:
Owing to the substantial changes in behavior of an
electrolytic powder cell when its size is increased, it is
advisable that, when such a process is advised in the
laboratory, it should be operated as a unit cell with fullsized electrodes before an attempt is made to design the
final plant.
Structural design factors involve taking decision upon
the size and nature of the electrodes, whether they
should be stationary or rotary, or be sheets, tubes or
rods, etc., whether the cathodes should be lifted out of
the cell for scrapping or not, whether the scrapping
should be manual or mechanical.
Other problems concern with the corrosive nature of the
electrolyte: such as tank construction and linings,
contacts, electrolyte handling, cooling or heating, used
anode treatment, etc.

After-treatment:
An electrolyte powder is generally in a reactive
condition, and is also wet with reactive electrolyte, there
are considerable problems in washing and drying it and
bringing it to a dry powder which is not only low in
oxide but reasonably stable on storage.
For example, with electrolytic iron powder, it was found
necessary to wash the cathode deposit with water, 2 %
H2SO4, water, dilute citric acid, water, dilute ammonia,
and finally with distilled water before filtering, and then
moistening with acetone before drying. Even then it is
recommended that the powder should be annealed in
hydrogen to reduce the oxide content.

Tyrrell, with copper powder, recommends annealing in a reducing

atmosphere. He found, however, that treating the powder in a cracked
ammonia atmosphere often led to rapid subsequent deterioration on
storage. He recommended treating the powder with suitable waterrepellent chemicals and indicated that stearic acid dissolved in ammonia
was suitable for a commercial process.
Many manufacturers avoid washing and drying difficulties by
annealing the powder in a reducing atmosphere.
When a brittle electro-deposit is the first product, annealing may be
absolutely necessary in order to produce a powder having reasonable
pressing qualities, and is customary among iron powder producers.
Owing to the reactive nature of many electrolytic metal powders,
difficulties are frequently observed in preventing them from oxidizing or
corroding on storage. It is customary, at least with copper powder, to add
corrosion inhibitors to the powder.

METAL POWDER TESTING

Characterization of Metal Powders:
Quality monitoring
The following steps are involved in P/M prior to
processing into compact shape:
a) Powder characterization and testing
b) Powder handling and mixing

a) Powder Characterization and Testing:

1. Powder sampling
2. Chemical Testing
i) Oxygen content of the powder
ii) Acid insoluble content of powders
3. Particle-related vs mass-related properties
4. Particle size and particle size distribution
i) Sieving
ii) Microscopic sizing
iii) Sedimentation methods
iv) Coulter Counter and particle analysis
by light obscuration
v) Laser light scattering

5. Particle shape and structure

6. Specific surface area
7. Characteristics determining the processing behavior of metal
powder:
i) Flow rate and apparent density
ii) Compactibility
iii) Dimensional changes of powders due to
sintering
b) Powder mixing and handling
1. Special precautions in handling and storing metal powders
2. Powder Mixing
i) Mixing and demixing
ii) Mixing apparatus

PARTICLE SHAPE:

Figure shows various possible particle shapes of powders.

Spherical powders show excellent flow properties but give
poor green strength as compared to irregular powders.
Water atomization ------ ranging from near spherical to
highly irregular.
Gas atomization --------- spherical powder particles.
The reactivity of the metal or alloy essentially determines
the particle shape. If the alloy-water reaction produces a
strongly adherent film then irregular particles are formed.
Spherical shapes are produced when the oxide formed are
highly fusible at the melting point of the alloy as they have
no strength to over-come the forces of surface tension.
High melting metals/alloys have tendency to form
spherical particles because of long freezing times.
Very short freezing times for low melting metals/alloys
tend to form highly irregular particles.

Table shows Particle Shape and the Method of Powder Production

ONE DIMENSIONAL
Acicular
Irregular Rod-like
Chemical decomposition
Chemical decomposition
Mechanical comminution
TWO DIMENSIONAL
Dentritic
Flake
Electrolytic
Mechanical comminution
THREE DIMENSIONAL
Spherical
Rounded
Atomization
Atomization
Carbonyl Fe
Chemical decomposition
Precipitation from a liquid
rregular
Porous
Atomization
Reduction of oxides
Chemical decomposition
Angular
Mechanical disintegration
Carbonyl Ni

Powder Properties:
Processing conditions and final sintered properties are
determined to a very large extent by the characteristics of
the powder, such as;
chemical composition
particle size and size distribution
particle shape
structure
surface condition

Sampling of Powders:
Standard methods
ASTM Committee B-9
MPIF Standard Committee (Metal Powder Industries

Federation)
ASTM Standards B215
MPIF Standard 1
A representative sample of the whole lot
Samples from the entire cross section of the stream of
powder.
Representative sample from a shipment consisting of
several drums.
Thieve sampling
Thieves are devices to take samples from different

CHEMICAL TESTS
a) Hydrogen Loss Test:
) ASTM standard E 159, MPIF standard 2
for the so-called hydrogen loss of Cu, W and Fe powder
) A sample of powder is heated in a stream of hydrogen
for a given length of time and at a given temperature.
) Loss of weight ---- an approximate measure of the
oxygen content of the powder.
) Hydrogen loss values may be lower than the actual
oxygen content -------- Oxides not reduced by hydrogen
under the test conditions such as SiO2, Al2O3, CaO, etc
)

The hydrogen loss value may be higher than the actual

oxygen content in the presence of elements forming
volatile compounds with hydrogen, i.e. S or C.

 Some metals volatile at the test temperature, i.e., Zn, Cd and

Pb.
To avoid measuring the content of C, S, or volatile metals in
the metal powder, a modified hydrogen loss test is used.
The amount of water vapor produced by heating in a stream
of dry hydrogen is determined by titration.
Total amount of oxygen in a metal powder including oxygen
in refractory oxides, fuse a sample in a small single-use
graphite crucible under a flowing inert atmosphere at a
temperature of 2000 oC or higher.
The oxygen is released as CO and measured by infrared
absorption or alternatively converted to CO2 and measured
by a thermal conductivity difference.

Acid Insoluble Content of Cu and Fe Powder:

Samples of Fe powder are dissolved in HCl and those of
Cu in HNO3 under specified conditions.
The insoluble matter is filtered out, ignited in a furnace and
weighed.
Silica, alumina, clays and other refractory materials
In Fe powder, the acid insoluble may also include insoluble
carbides.

Particle Size and Particle Size Distribution

Methods:
(a) Sieving
(b) Microscopic Sizing
(c) Methods based on Stokes Law
i) the Roller Air Analyzer
ii) the Micromerograph
iii) Light and X-ray (Sedigraph) Turbidimetry
(d) Coulter Counter and Particle Analysis by Light
Obscuration
(e) Laser Light Scattering; the Microtrac Particle Analyzer
(f) Zetasizer Nanoparticle size analyzer

Sieving:
ASTM sieves size,
and U.S. standard
sieve designation,
m
180 (No 80)

Tyler sieves size,

and Tyler sieve
series designation,
m
175 (80 mesh)

150 (No 100)

149 (100 mesh)

106 (No 140)

104 (150 mesh)

75 (No 200)

74 (200 mesh)

45 (No 325)

44 (325 mesh)

Figure: Schematic of sieve

series stacked in order of size

Figure: Stacked sieves on a

shaker with rotary
and tapping action

Figure: Sieved size of an irregularly shaped

particle

Methods Based on Stokes Law:

Sedimentation and Elutriation
Stokes Law gives the settling velocity of spherical
particles with a diameter x and a density in a fluid
medium with density F and viscosity
= g ( - F ) / 18 * x2
Where g is the gravitational constant.
** Particles which are not spherical will also settle. Their
Stokesian size is defined by the diameter of a sphere of
the material which has the same settling velocity as the
irregular powder particle.

 Convection currents in the suspending fluid must be

avoided.
The relative rate of motion between the fluid and the
powder particles must be slow enough to guarantee
laminar flow, which means the Rynolds number should be
less than 0.2
x F /
Where x is the particle size, is the settling velocity, F
the density of the fluid and its viscosity.
The particles in the suspension must be perfectly
dispersed and the suspension must be dilute enough to
guarantee independent motion, which means maximum
concentration of about 1 % by volume of particles in the
suspending medium.

METAL POWDER
PROCESSING TECHNIQUES
Compaction of Metal Powders:
Different ways of consolidation of metal powders;
(A) With application of pressure which includes
i) Uniaxial pressing (single action or double action pressing)
ii) Isostatic pressing
iii) Rocking die compaction
iv) Powder rolling
v) Powder extrusion
vi) Powder swaging
vii) Powder forging
viii) Powder Injection Molding
(B) Without applying pressure such as;
i) Slip mixing or slip casting
ii) Vibrational compaction

 Consolidation generally occurs in three stages

(a) rearrangement of particles.
(b) particles contacting by plastic deformation.
(c) mechanical locking and cold welding of particles due
to surface shear strains.

It is, therefore, some time easier to cold compact irregular

particles than spherical powder particles.

 Main variables in pressure compaction are:

(a) Method of compaction
(b) Compaction pressure, time and temperature
(c) Rate of compaction
(d) Compacting atmosphere
(e) Lubricants and other additives of the mix, and
(f) Die design
()The main objectives obtained during pressing are:
(1) To achieve the required part shape.
(2) To obtain the required green density.
(3) To secure sufficient green strength to permit safe handling of
the part.
(4) To provide particle-to-particle contact which is necessary for
sintering.

The basic types of compacting presses are:

(i) Mechanical (single punch or rotary type) presses.
(ii) Hydraulic presses.
(iii) Hybrid-type presses (mechanical presses may make use of
auxiliary pneumatic or hydraulic devices).

 For pressing
The powder metal must first fill the die orifice.
Filling may be done by hand or automatically from the
press-hopper.
A constant volume or constant weight may be used.
Vibration filling is introduced to create denser packing to
avoid bridging and high porosity defects.
Pressing may be done automatically.
The pressure may be applied along more than one axis using
various punch and die sets designed to minimize defects.
Ejection after pressing may be carried out automatically or
by hand.


(i)
(ii)
(iii)
(iv)
(v)

Minimum requirements for any powder metal press:

Adequate total pressure capability in the direction of
pressing and sufficient part ejection capability.
Controlled length and speed of compression and ejection
strokes.
Adjustable die fill arrangements.
Synchronized timing of press strokes.
Material feed and part removal systems.

 General classification of powder metallurgy parts:

1) Class I parts with a diameter (or thickness) up to

65 mm and one level parts of any contour that can
be pressed with a force from one direction.
2) Class II parts are single level components of any
thickness and any contour that must be pressed
from two directions.
3) Class III parts are two level components of any
thickness and contour that must be pressed from
two directions.
4) Class IV parts are multilevel components of any
thickness and contour that must be pressed from
two direction.

Compacting Presses and Attachments:

The presses systems used are;
(a) Single action press system consisting of:
i) a die to form the outer contour of the part;
ii) an upper punch to form the top surface of the part;
iii) a lower punch to form the bottom surface of the part;
iv) if required, core rods to form any through holes
(for class I parts).

(b) Double action opposed ram system consists of

a die, upper punch, lower punch and core rods (for class I
and class II parts).
(c) Double action floating die system consists of
moving upper punch, stationary lower punch, moving die
table and core rods (for class I IV parts).
Further during compaction tooling materials, clearances and
tolerances require expertise and special attention is paid to
(i) die design; (ii) die materials; (iii) punch; (iv) carbide
inserts; (v) tolerances, clearances and finishes.

Forming and sintering in one step

The simplest forming route for a metal powder is loosepowder sintering which is used for forming spherical
powder.
In this process the metal powder is filled loosely or shaken
into the mould by vibration and subsequently sintered in the
mould.
The mould can be made of steel or graphite and can be used
repeatedly.
Powders which are difficult to compact are often formed by
simultaneous application of pressure and temperature
(pressure sintering).

Forming and Sintering in Separate Process Steps

Axial pressing
The powder is charged by volume filling into a closed tool
consisting (in principle) of three parts; a die and an upper and
a lower punch, and subsequently subjected to a pressure using
mechanical or a hydraulic press.
The cycle begins with the tool in the filling position (1) in
which the upper and the lower punches are retracted so that a
defined filling space arises. The tool is filled with powder
from the filling shoe, the quantity of powder being determined
by the volume of the die cavity at this stage (2).

 The height of the filling space is determined by the apparent

density (filling volume) of the powder and by the required
final density of the component.
It usually is equal to 2.2 to 3 times the height of the
component.
After finishing the filling operation the powder is
compacted by the counter movement of the lower and the
upper punches until the tool has reached the pressing
position (3 & 4).
After completion of the pressing step the upper punch is
withdrawn and the compact is ejected by moving the lower
punch upwards (5). The ejected component is pushed away
from the die by the filling shoe (6), and the tool is again
ready for a new pressing cycle.

Compaction

Uniaxial Pressing

The ejection system

During compaction according to the ejection system with
two punches moving in opposite direction (figure B) the die
remains fixed and the two punches carry out the
compaction. The compact exhibits a symmetrical density
distribution with a neutral zone in the middle. The counter
movements of the punches are effected by cams and toggle
joints in the case of a mechanical press and by separately
controlled upper and lower cylinders in the case of a
hydraulic press.

ISOSTATIC PRESSING
The metal powder is compacted uniformly in all directions
so that the compact becomes an accurate scale down of the
mould.------- uniform density ------- a homogeneous
microstructure
For this purpose the powder is sealed in a flexible envelope
and the assembly (mould-powder) is immersed in a fluid
which is pressurized.
There are virtually no residual stresses in the compacted
material, because there is no die wall friction.
Figure1 shows the use of formers and use of containers with
holes for support purposes.

Fig. 1: Examples of use of (a) container with holes and

(b) (c) formers for producing shaped components by
isostatic pressing.

Two types of processes:

i) Cold Isostatic Pressing
ii) Hot Isostatic Pressing
* Cold Isostaic Process ----- two methods are used :
(a) free mould or "wet bag" process (Figure 2) is suited for
(i) batch scale production;
(ii) the mold is filled and sealed outside the pressure vessel.
(iii) After the mold is introduced in to the pressure vessel, it is
completely immersed in the pressure medium, usually water
containing lubricating and corrosion-preventive additives;
(iv) complex parts;
(v) research and prototype work;
(vi) several moulds in one run-even with;
(vii) differing shape, i.e. parts of different sizes and shapes that
require the same process parameters can be pressed in the
same cycle.

a) Powder fill by weight or volume.

b) Filling of the mould from the top.

c) Top lid put on the mould container.

d) Mould is placed inside the pressure vessel.

e) Top lid put on the pressure vessel after necessary

evacuation and filling with the pressurizing medium.
f) Top lid removed after required isostatic compaction for
removal of the mould.

(b) fixed mould or "dry bag" process (Figure 3) which is

characterized by
(i) envelope is permanently fixed into the pressure vessel,
(ii) After the elastomeric mold is filled with powder, pressure
is applied by introducing pressurized oil between the
fixed mold and the vessel wall,
(iii) only one compact at a time is used,
(iv) more simple shapes are made and
(v) more suited for mass production and faster production
rates.

Fig.3: Schematic of equipment for dry-bag isostatic pressing.

Pressure Generators
Pressure is generated in the pressure medium through the
use of air-driven and hydraulically driven pumps and
pressure intensifiers.
The pressure medium typically is oil for dry bag processes;
water containing additives (water-soluble oil or rust
inhibitors) is used for wet bag processes. A filtering system
should be included with all systems to protect the pressuregenerating equipment from particulate contamination.
Depressurization Systems. Depressurization can be
accomplished with a single metering valve.