POWDER METALLURGY (P/M)

-Art & science of manufacturing useful articles from metal powders and of
producing those metal powders
1 Historical Development Of P/M
Origin - ~ 5000 years ago
Examples - Iron implements of Egyptian civilization existed around 3000
B.C.
- Iron pillar in Delhi of 300 A.D.
Scientific development – in first half of 19th century with the published
work of Wollaston at about 1829 – details of producing malleable Pt from Pt
sponge powder – obtained by igniting ammonium chloroplatinate and
breaking it in a wooden mortar to prevent burning of powder particles. Wash
the black powder and compress while wet. Heat the compact mass to
redness, hammer & forge while hot to usable shape. Visualized the process
to be dependent on such factors as particle size, purity, compacting to high
density & high temperature treatment to produce a coherent metallic mass
1910 – Coolidge process for the production of ductile tungsten at R.T. –
prepare the briquettes in the form of small ingots, sintering in a protective
atmosphere – repeated hot working to obtain ductile metal as a rod – finally
draw down to a ductile W wire for incandescent light bulb filaments
After 1910 – Cemented refractory materials for drawing W wire
Other applications perfected before World War II – self-lubricated
bearings, brushes, filters, powdered iron cores, iron-nickel alloys
(permalloy) magnets
Brief history – Table 1.1
Present attention – more complex multiphase alloys & exotic materials as
used in nuclear & space applications
2. Reasons for Using P/M
2.1 Advantages of powder metallurgy process
Process advantages
(i) Eliminates or minimizes machining (little or no scrap)
(ii) Efficient materials utilization – above 95%
(iii) Enables close dimensional tolerances – near-net shapes possible
(iv) Produces good surface finish
(v) Provides option for heat treatment, for increasing strength or
enhanced wear resistance and plating for improving corrosion
resistance
(vi) Facilitates manufacture of complex shapes, which would be
impractical with other metal working processes
(vii) Suited to moderate to high-volume production requirements
(viii) Components of hard materials which are difficult to machine
can be readily manufactured, e.g. tungsten wires for
incandescent lamps
(ix) It is possible to produce components in pure form.
(x) Energy-efficient
(xi) Environment-friendly
Metallurgical Advantages
Enables the production of:
(i) Powders with uniform chemical composition with the desired
characteristics
(ii) Elemental and pre-alloyed powders
(iii) Unique compositions including non-equilibrium ones
(iv) Wide variety of materials – metals and alloys of miscible and
immiscible systems, refractory metals, ceramics, polymers and
composites
(v) Parts with controlled porosity
Commercial Advantages
(i) Can be oil-impregnated to function as self-lubricating bearings.
Can be resin-impregnated to seal interconnected porosity to
improve density or can be infiltrated with a lower melting point
 metal for greater strength and shock resistance, and for making
electrical contacts
(ii) Cost-effective
(iii) Offers long term performance reliability in critical applications

3 Metal Powder Manufacturing Techniques And Powder

Characterization
3.1 Metal powder manufacturing techniques
I Mechanical Methods
a) Machining
To produce filings, turnings, scratchings, chips etc.- pulverized by crushing
and milling
Coarse and bulky powders
Production of Mg powders for pyrotechnic applications, Be powders, Ag
solders, and dental alloys
Irregular shape

b) Crushing
Disintegration of oxides and brittle materials
Equipment – stamps, hammers, jaw crushers, or gyratory crushers
Ferrous and non-ferrous alloys – heat treated – brittle materials
Ti, Zr, V, Nb, and Ta when heated to moderate temperature in H2 – brittle
hydrides
Angular shape – comminuted by milling to required fineness

c) Milling
Comminution of brittle, friable, tough and hard materials and pulverization
of malleable and ductile metals
Application of impact force
Equipments – ball mill, rod mill, disk mill, eddy mill, vortex mill, etc.
In ball milling, a set of hard wear resistant bodies are used.
Mills can be rotated or vibrated
Fig. 14 – Schematic diagram of ball mill

Material tumbled in a container together with large number of hard wear

resistant solid balls which by hitting the material, cause it to break down
Two types – rotary and vibratory
Latter – short time
Powder – less contaminated – smaller wear on balls and mills
Drums of rotary mills – stainless steel or steel lined with hard alloy plates
Balls – steel or hard alloy
Critical speed of rotation – for proper milling action of balls
Neither slow nor very high
Milling action will not be carried out correctly in the latter case because
centrifugal force – clinging of balls
Most intense grinding action at critical speed – balls lifted upto top part of
drum and fall down on material to be ground
In Hametag eddy mill, rotating fans impart a high velocity to the
particles so that they impact against each other
In microniser, high velocity jets of gas fling the particles against a
surface
 d) Shotting – Pour the molten metal through screens – droplets

are solidified into shots by free fall

e) Graining – Like shotting – material falling through sieve

collected in water
Powders – Cd, Bi, and Sb
II Chemical Methods
a) Reduction – usu. Oxides
Choice of reducing agents (CaH2 for stable oxides, C, H2, metal –
Al for Cr2O3, Mg & Na for TiCl4 & ZrCl4) – considerations –
thermodynamic, convenience, & economics
Reduction – normally a high temperature process giving sponge
metal
Powders – generally fine
Hoeganaes Process – The ore, coke breeze & limestone (to absorb
S). Mixture packed into refractory saggers & heated to 12000C.
Cake of iron sponge resulted pulverized to powder. For high
quality soft powder, pulverized powder annealed in H2, which
besides eliminating the effect of cold work due to pulverizing
operation, also lowers C & O2 contents
Pyron Process – carefully selected mill-scale is reduced with H2
Reduction usually carried out using continuous mesh belt furnaces
Batch type furnaces – for making small quantities – Fig.2.5
b) Thermal decomposition
Ni & Fe – by carbonyl method
Crude iron powder obtained by reducing crushed iron ore with H2 – reacted
with CO under pressure.
Fe + 5CO = Fe (CO) 5
Gaseous Fe (CO) 5 formed is decomposed subsequently by injecting into a
heated free space. Fine spherical particles collect at the base of decomposer
& CO is drawn off for re-use. For electronic core powders, additive to other
powders for sintering
Ni(CO)4 boils at 430C- produced by allowing CO to pass over spongy or
powdered metal at suitable temperature (200-2100C) & pr.(70-400 atmo.).
Ni(CO)4 is led into a heated chamber (150-4000C) at one atmosphere where
a cloud of microscopic condensed particles is first deposited. These particles
whose size has been found to be about 0.01 μ serve as nuclei on which more
condensing metal is built up until quite large shot is formed.
200 atm. ΔH
Ni + 4CO Ni(CO)4 Ni + 4CO
200-2700C

CO is then recycled & employed again to produce more carbonyl liquid to

continue the process. For sintered magnets, nickel steels, nickel silver parts.
Particle size 2-20 μ. Fe – spherical, Ni – irregular
Pure powder
c) Hydride-dehydride process
Decomposition of hydride - high-purity powder
For the production of reactive metals – Ti, V, Nb, Hf, Zr, Th, and U
Two stages:
First stage – metal converted to hydride – reaction with H2 – suitable
temperature under pressure
Ti – reaction – 3000C-5000C
Ti + H2 = TiH2
Hydride – brittle – crushed to powder of required fineness
Second stage – hydride is decomposed to metallic powder by heating under
vacuum – same temperature – hydride was formed
TiH2 = Ti + H2
Also used for very fine U powder production
Process involves heating U alloy ingot at 3000C in H2 atmosphere
to form UH3
 UH3 reduced by heating under vacuum
3H2 + 2U = 2UH3
2UH3 = 3H2 + 2U
d) Precipitation from aqueous solution
(i) By precipitating a compound – hydroxide, carbonate or oxalate – heating
– decomposition
(ii) Metal – precipitated by addition of less noble metal
E.g. Cu by Fe from CuSO4 solution – very fine powder
e) Gaseous reduction method
A sulphide concentrate is leached with NH3 & air under pressure.
Suphides are oxidized & nonferrous metals react with NH3 to form
amine ions such as [Ni(NH3)]2+. The residue containing SiO2, iron
hydroxide etc. is separated out. Copper is then precipitated from
the liquid so that the remaining solution containing only Co & Ni
reacts with H2 to precipitate Ni metal in the pure state until the
concentration of both in solution reach about the same value.
Due to considerably higher thermodynamic activity & faster rate of
reduction, reduction reaction of Ni is favoured in the mixed
system. When precipitating Ni, Ni powder particles as seed
materials are introduced which are held in suspension by agitation.
Washed free from last traces of salts & then dried in H2 to remove
O2, C, & S.
f) Precipitation from fused salt
Reactive metals
For Zr, ZrCl4 salt mixed with equal amount of KCl and some
Mg. Mg replaces Zr when heated to 7500C and powder particles
of Zr settle at base of treatment chamber
 Another method - ZrCl4 vapour introduced into salt bath of
NaCl & KCl
Other metals – Be & Th
g) Reduction-condensation method
E.g. (a) Very fine ZnO mixed with powdered charcoal and heated
until Zn vapour is formed
Zn vapour is condensed in cooler regions of retort
Because of high-oxygen content, powders are not considered
suitable for P/M purposes
Possible to obtain high purity - second condenser
(b) Mg powder – reducing MgO with calcium carbide followed by
collection of Mg vapour in oil
III Physical Methods
Use of physical means
Major methods – electrodeposition and atomisation
a) Electrolytic Deposition – Aqueous or fused salt

Mainly used – Cu & Fe

Sulphate solutions
Addition of NH4Cl increases conductivity and reduces oxidation
Cu powder
Dil. acidic CuSO4 – high C.D.
Plant usu. attached to an electrolytic Cu refinery from which cast
anodes are obtained.
Copper sulphate and sulphuric acid
Cathodes – Al, Cu, or Pb in sheet or rod form.
Reactions
At anode:
 Cu = Cu++ + 2e-
At cathode:
Cu++ + 2e- = Cu
As deposited – dendritic shape. Washed carefully to remove excess
electrolyte. After drying, annealed in either cracked NH3 or
partially burned town gas atmosphere. Annealing operation results
in some agglomeration & the resulting cake is pulverized by
milling. For porous bronze bearings, motor brushes, friction
materials, contacts
In the case of iron, anode – low carbon steel or ingot iron
Cathode – s.s.
Fe powder deposit – pulverized by milling in hammer mill
Milled powders annealed in H2 to make them soft
Electrolytic powders crystalline – dentritic – low apparent density and
flow rate favourable for pressing
Preparation of alloy powder – possible – use o mixture of electrolytes
Electrolytic bronze and brass – produced
Fused salt electrolysis – at a temperature below m. p. of metal
Deposition – small crystals with dendritic shape
Powders – Th, Ta, V
Depending upon processing conditions, final product – three different
forms:
(i) Hard brittle layer - milled to obtain powder (e.g. Fe)
(ii) Soft spongy – loosely adherent and easily removed by scrubbing
(iii) Direct powder – collects at bottom
Last two methods – for production of large quantities
C.D. & acidity low – brittle deposit
 C.D., acidity & viscosity high & concentration low – loose fluffy
deposit
Selection of cathode – complete removal – great importance for continuous
commercial removal
Highly polished and smooth surfaces – deposit stripped by flexing or
scrubbing or by rotating or by rapid circulation of bath
Advantages:
(i) High purity with excellent compactibility and sinterability
(ii) Allows production of wide range of powder by altering bath
composition
Disadvantages:
(i) Time consuming
(ii) Powder must be washed thoroughly, dried and annealed to avoid
rapid oxidation, which adds to operating cost
(iii) Handling and processing involves toxic chemicals resulting in
pollution of work place
(iv) Waste disposal another problem
b) Atomization

One of the most widely used method –powders of metals and alloys
Steps – melting, atomizing molten stream and solidifying the droplets
Stream of molten metal is mechanically disintegrated by a jet (or jets) of
high pressure fluid
Mannesmann Process – Molten low Si CI atomized by a spiraling annular
jet of compressed air. Oxidation of the particle surface occurs but with
careful control of O2 & C contents, relatively pure powder can be produced
by a heat treatment at 8500C. More expensive than Hoeganaes process but
has fewer non-metallic inclusions & therefore less abrasive to press tools
 Factors affecting powder properties – metal temp., water pressure
and tundish nozzle diameter
Irregular to smooth rounded dense particles. Purity – high, 99.5+,
wide range of sizes.
E.g. S.S., brass, Al etc.

Table 1 Production Methods vs. Powder Characteristics

Method Powder Characteristics
Purity Shape Size
1. Reduction Medium; 98.5- Irregular, spongy Generally fine
 99.0+
2. Precipitation High; 99.2-99.8 Irregular Very fine
3.Electrolytic High, 99.5+ Dendritic All sizes
deposition
4. Thermal High; 99.5+ Spherical 2-20μ
decomposition
5. Mechanical Medium; 99.0+ Flaky All sizes
Methods
6. Atomization High; 99.5+ Irregular to Wide range of
smooth rounded sizes – coarse to
fine

3.2 Powder characterization

Primary Properties – Composition, Particle Size, Shape & Structure
Characteristics – Specific Surface, Apparent Density, Flow Characteristics,
Compacting Characteristics, Sintering Characteristics
Composition – Affects final product properties & processing
E.g. – Compaction depends on plasticity & rate of strain hardening –
both depend on chemical composition
Alloy content & impurities affect diffusion rates & formation of liquid
phases at the sintering temp.
Chemical analysis – All established techniques
E.g. – Oxygen determination by wt. loss or wet analysis
 X-ray analysis – To determine e.g. ferrite in austenitic s. s., detection
of W2O in WC, oxide phase in metal powders

Particle Size, Shape & Specific Surface – Interrelated

Influence both compaction & sintering
For automatic compaction – high A.D. & good flow characteristics –
hence coarse powders of spherical shape
For good compacting characteristics – irregular shaped particles
For sintering – fine particles of irregular shape
Particle size – Measurements

1. Using microscope – optical or electron

(0.1-100μ) (0.001-10μ)
2. Sieving
3. Sedimentation – based on Stoke’s law
 d = [18ηu]1/2/ [(ρp – ρf)g]1/2
- using balance
- pipette method
- hydrometer
- manometer
- turbidimetry
- centrifuging
4. Elutriation
Specific surface – by sorption & permeametry
Sorption – Adsorb a suitable fluid such as N2 in
monomolecular layer. Find the amount adsorbed. Calculate the no. of
molecules – find the total area covered from a knowledge of the area
covered by a single molecule – done in B.E.T. (Brunauer, Emmett, & Teller)
apparatus
Permeametry – principle – resistance offered to fluid flow by a
powder bed is proportional to S.A.
Particle shape
- by microscopic examination
- expressed by shape factor = length/breadth or S.A./Size

Structure – microstructure – no. of phases, amount of phases & distribution

of phases + porosity (internal) – indicate powder’s likely behaviour during
pressing & sintering
- determined by composition & method of production
- examination follows well-established techniques
Flow rate – by Hall flow meter – 50 gms of sample – flow rate expressed in
sec.
For powders which are not free flowing, Carney funnel having orifice dia &
length double that of Hall flow meter can be used
Funnel material – usu. brass
Apparent density
Mass per unit volume of loose powder
Governed by chemical composition, particle shape, size, size distribution,
method of manufacture as well as shape and surface conditions
Influences pressing
The lower the apparent density, the longer – compression stroke – deeper
dies required
Powder poured through Hall flowmeter into density cup – 25+/-0.5 ml.
Excess powder leveled off
Cup tapped
Compacting characteristics
1. Compression ratio = volume of powder poured/ volume of pressed

part
= G.D. /A.D.
2. Compactibility – minimum load necessary to ensure a green

handleable compact. Quantitatively, the minimum pressure required to

produce compact of given green strength
3. Green strength
(a) Rattler test – tumble 5 std. specimens in a cylindrical barrel of

14# bronze gauze of std. size at 87 rev. /min. for 1000

revolutions. Loss in wt. as a percentage of their original wt. is a
measure of their abrasion resistance
(b) Transverse rupture strength
S = 3WL/2bd2
W = applied load, b = width of specimen
IS: 4842
4. Green density – for regular shape – calculated from mass &

dimensions
For complex shapes – by weighing in air and water
 5. Green spring – radial & longitudinal expansion on ejection owing to

elastic recovery of residual stresses – depends on the powder, load,

elastic properties & design of die – important to fix dimensions for
precision parts
Sintering characteristics
1. Shrinkage (Growth) = (Change in length/ original length) x 100

2. Sintered density – determination in the same way as for G.D.

% porosity (P) = (Dt - Ds) x 100/Ds

3. Transverse rupture strength
4. Radial crushing strength
W = Radial crushing strength
= KLT2/ (D – T)
 K = Strength constant – dependent upon density & composition
L = length
T = thickness
D = Outside dia.
5. Microstructure – to determine amt., size & distribution of porosity,
homogeneity, distribution of phases, grain size, presence of oxides &
other inclusions