Materials Science

and Metallurgy
S Nagappa
Assistant Professor,
Dept. of Mechanical Engineering, VIIT
POWDER METALLURGY
 INTRODUCTION
Powder Metallurgy is defined as the art and science of producing metal
powders and making semi-finished and finished objects from individual, mixed
or alloyed powders with or without the addition of nonmetallic constituents.
Steps involved in the Powder Metallurgy:
 Powder Production - Powders are manufactured by various methods
and the powder from each method has typical properties.
 Compaction – Compaction in metal dies is one of the most important
method for shaping of metal powders.
 Sintering – Sintering is carried out to increase strength and hardness of
a green compact, performed at controlled atmosphere to bond atoms
metallurgically; Bonding occurs by diffusion of atoms.
 Secondary and other finishing operations – These are finishing
operations

Powder Metallurgy is also one of the mechanical treatment which involves conversion
of metal or alloys into the fine powder and converting them into desire shape.
INTRODUCTION
 Advantages
 Efficient material utilization
 Enables close dimensional tolerances – near net shape possible
 Good surface finish
 Manufacture of complex shapes possible
 Hard materials used to make components that are difficult to
machine can be readily made – tungsten wires for incandescent
lamps
 Environment friendly, energy efficient
 Suited for moderate to high volume component production
 Powders of uniform chemical composition, reflected in the
finished part
 Wide variety of materials - miscible, immiscible systems;
refractory metals
 Parts with controlled porosity can be made
 Limitations
 Fine powders of some of the metals like Mg, Al, Zr, Ti
etc. are likely to explode and cause fire hazards when they
come in contact with air and hence, they should be
preserved carefully.
 Not suitable to manufacture small number of components
because high cost of powder material & tooling
 Complex shaped parts can not be manufactured with ease
by P/M
 P/M parts have poor corrosion resistance because they are
porous.
 Less well known process
 Applications
 Automotive applications – In motor car industry, porous bearings are used for
starters, wipers, sliding doors, dynamos, clutches, and brakes of cars. Sintered
gears are widely used in cars and trucks.
 Defense Applications – Metal powders play an important role in military and
national defense systems, These powders find use in rockets, missiles, cartridge
cases, bullets and military pyrotechnics such as tracers, incendiaries.
 High temperature applications – Components made of W, Mo and Ta by P/M
are widely used in the electric light bulbs, fluorescent tubes, radio values,
mercury arc rectifiers and X-ray tubes in the form of filaments. Refractory
metal carbides are used for dies, rolls, cutting tools, etc at high temperatures.
 Aerospace Applications – Metal powders plays an important role in rockets,
missiles, satellites and space vehicles. Metal powders of Be, Al, Mg, and Zr,
are used as solid fuels in rockets and missiles.
 Atomic Energy Applications – Dispersion strengthened materials are used in
atomic reactors, magneto dynamic generators, high temperature gas turbines
and computers.
 Other applications – Parts in clocks and timing devices, typewriters, cemented
carbides, refractory metals etc.
 Metal Powder Production Methods
 Powder Metallurgy begins with the production of metal and non
metal powders.
 There are various methods for the production of powders and each
method gives a different size, shape and distribution and have
different characteristics.
 The various processes are used to produce the powders:
 Mechanical Methods - Cheapest of the powder production
methods; Involve using mechanical forces such as compressive
forces, shear or impact forces Ex. Milling
 Chemical Methods – Make use of chemical reactions Ex.
Reduction
 Physical Methods – Electrolytic Deposition
 MILLING
During milling, impact, attrition, shear and compression
forces are acted upon particles.
Main objective of milling:
 Particle size reduction
 Particle size growth
 Shape change
 Agglomeration (Putting the particles together)
 Solid state alloying (Mechanical Alloying)
 Solid State mixing or blending
 Modification of material properties
 MILLING
Mechanism of milling:
Changes in the morphology of powder particles during
milling results in the following events.
 Microforging - Individual particles or group of particles
are impacted repeatedly so that they flatten with very
less change in mass.
 Fracture - Individual particles deform and cracks initiate
and propagate resulting in fracture
 Agglomeration - Mechanical interlocking due to atomic
bonding.
 Deagglomeration - Breaking of agglomerates
 Milling Equipment
The equipment's are generally classified as crushers & mills
Crushing - for making ceramic materials such as oxides of metals
Grinding – for reactive metals such as titanium, zirconium, niobium, tantalum
Different types of grinding equipment's/methods are shown in the figure
 Ball Mills
 Ball mill contains cylindrical vessel rotating horizontally along the axis. Length
of the cylinder is more or less equal to diameter.
 The vessel is charged with the grinding media. The grinding media may be made
of hardened steel, or tungsten carbide, ceramics like agate, porcelain, alumina,
zirconia.
 During rolling of vessel, the grinding media and powder particles roll from some
height. This process grinds the powder materials by impact or collision and
attrition.
 Milling can be dry milling or wet milling. In dry milling, about 25 vol% of
powder is added along with about 1 wt% of a lubricant such as stearic or oleic
acid.
 For wet milling, 30-40 vol% of powder with 1 wt% of dispersing agent such as
water, alcohol or hexane is employed.
 Optimum diameter of the mill for grinding powders is about 250 mm.

Critical number of Revolutions Nc = (60/2π) (2g/D)1/2

 Vibratory Ball Mill
 Another type of ball mill in which high amount of energy is imparted to the particles and
milling is accelerated by vibrating the container.
 The comminution is due to vigorous action of multitude of grinding bodies moving
inside the container in different directions at varying speeds as a result of the applied
vibratory loads.
 This mill contains an electric motor connected to the shaft of the drum by an elastic
coupling. The drum is usually lined with wear resistant material.
 During operation, 80% of the container is filled with grinding bodies and the starting
material.
 Here vibratory motion is obtained by an eccentric shaft that is mounted on a frame inside
the mill. The rotation of eccentric shaft causes the drum of the vibrating mill to oscillate.
 In general, vibration frequency is equal to 1500 to 3000 oscillations/min. The amplitude
of oscillations is 2 to 3 mm.
 The grinding bodies is made of steel or carbide balls, that are 10-20 mm in diameter.
 The mass of the balls is 8-10 times the charged particles.
 Final particle size is of the order of 5-100 microns.
 Fluid energy grinding or Jet milling
 The basic principle of fluid energy mill is to induce particles to collide
against each other at high velocity, causing them to fracture into fine
particles.
 Multiple collisions enhance the reduction process, therefore multiple jet
arrangements are incorporated in the mill design.
 The fluid used is either air about 0.7 MPa or stream at 2 MPa.
 In the case of volatile materials, protective atmosphere of nitrogen and
carbon-di-oxide is used.
 The pressurized fluid is introduced into the grinding zone through
specially designed nozzles which convert the applied pressure to kinetic
energy.
 Materials to be powdered are introduced simultaneously into the
turbulent zone.
 The velocity of fluid coming out from the nozzles is directly proportional
to the square root of the absolute temperature of the fluid.
 Fluid energy grinding or Jet milling
 If further powdering is required, large size particles are separated from
the rest centrifugal forces and re-circulated into the turbulent zone for
size reduction.
 Fine particles are taken to the exit by viscous drag of the exhaust gases to
be carried away for collection.
 This Jet milling process can create powders of average particle size less
than 5 μm
 Other Mechanical Methods
Machining:
Mg, Be, Ag, solder, dental alloy are specifically made by machining.
Turning and chips thus formed during machining are subsequently crushed
or ground into powders
Shotting:
Fine stream of molten metal is poured through a vibratory screen into air or
protective gas medium.
When the molten metals falls through screen, it disintegrates and solidifies
as spherical particles.
These particles get oxidized. The particles thus obtained depends on pore
size of screen, temperature, gas used, frequency of vibration.
Metal produced by the method are Cu, Brass, Al, Zn, Sn, Pb, Ni.
Graining:
Same as shotting except that the falling material through sieve is collected
in water
Powders of cadmium, Bismuth, antimony are produced.
 Atomization
 Atomization is one of the most widely used method of making powders of metals and
alloys.
 Atomization involves the use of high pressure fluid jets to break up a molten metal
stream into very fine droplets, which then solidify into fine particles.
 High quality powders of Al, brass, iron, stainless steel, tool steel, superalloys are
produced commercially.
Mechanism of atomization:
In conventional (gas or water) atomization, a liquid metal is produced by pouring molten
metal through a tundish with a nozzle at its base.
The stream of liquid is then broken into droplets by the impingement of high pressure gas or
water.
This has five stages
 Formation of wavy surface of the liquid due to small disturbances
 Wave fragmentation and ligament formation
 Disintegration of ligament into fine droplets
 Further breakdown of fragments into fine particles
 Collision and coalescence of particles
 Atomization
The interaction between jets and liquid metal stream begins with the creation of small
disturbances at liquid surfaces, which grow into shearing forces that fragment the liquid into
ligaments.
The broken ligaments are further made to fine particles because of high energy in impacting jet.
The liquid metal stream velocity, v = A [2g (Pi – Pg)ρ]0.5
where Pi – injection pressure of the liquid, Pg – pressure of atomizing medium, ρ – density of the
liquid
Types of atomization
Atomization of molten metal can be done in different ways depending upon the factors like
economy and required powder characteristics. At present, water or gas atomizing medium can be
used to disintegrate a molten metal stream. The various types of atomization techniques used are,
Water atomization: High pressure water jets are used to bring about the disintegration of molten
metal stream. Water jets are used mainly because of their higher viscosity and quenching ability.
This is an inexpensive process and can be used for small or large scale production. But water
should not chemically react with
metals or alloys used.
Gas atomization: Here instead of water, high velocity argon, nitrogen and helium gas jets are
used. The molten metal is disintegrated and collected as atomized powder in a water bath.
Fluidized bed cooling is used when certain powder characteristics are required.
Vacuum atomization: In this method, when a molten metal supersaturated with a gas under
pressure is suddenly exposed into vacuum, the gas coming from metal solution expands, causing
atomization of the metal stream. This process gives very high purity powder. Usually hydrogen is
used as gas. Hydrogen and argon mixture can also be used.
 Atomization
Centrifugal atomization: In this method, one end of the metal bar is
heated and melted by bringing it into contact with a non-consumable
tungsten electrode, while rotating it longitudinally at very high speeds. The
centrifugal force created causes the metal drops to be thrown off outwards.
This will then be solidified as spherical shaped particles inside an
evacuated chamber. Titanium powder can be made using this technique
Rotating disk atomization: Impinging of a stream of molten metal on to
the surface of rapidly spinning disk. This causes mechanical atomization of
metal stream and causes the droplets to be thrown off the edges of the disk.
The particles are spherical in shape and their size decreases with increasing
disk speed.
Ultra rapid solidification processes: A solidification rate of 1000C/s is
achieved in this process. This results in enhanced chemical homogeneity,
formation of metastable crystalline phases, amorphous materials.
 Atomization Unit
Melting and superheating facility: Standard melting furnaces can be used for
producing the liquid metal. This is usually done by air melting, inert gas or
vacuum induction melting. Complex alloys that are susceptible to
contamination are melted in vacuum induction furnaces. The metal is
transferred to a tundish, which serves as reservoir for molten metal.
Atomization chamber: An atomization nozzle system is necessary. The nozzle
that controls the size and shape of the metal stream if fixed at the bottom of the
atomizing chamber. In order to avoid oxidation of powders, the tank is purged
with inert gas like nitrogen.
Powder collection tank: The powders are collected in tank. It could be dry
collection or wet collection. In dry collection, the powder particles solidify
before reaching the bottom of the tank. In wet collection, powder particles
collected in the bottom of the water tank. The tank has to be cooled extremely
if used for large scale production.
During operation, the atomization unit is kept evacuated to 10-3 mm of Hg,
tested for leak and filled with argon gas.
 Atomizing mediums
The selection of the atomizing jet medium is based mainly on the
reactivity of the metal and the cost of the medium
Air and water are inexpensive, but are reactive in nature
Inert gases like Ni, Ar, He can be used but are expensive and hence
have to be recycled
Pumping of cold gas along with the atomizing jet, this will increase
the solidification rate
Recently, synthetic oils are used instead of gas or water, this yields
high cooling rate and lower oxygen content compared to water
atomized powders
Oil atomization is suitable for high carbon steel, high speed steels,
bearing steals, steel containing high quantities of carbide forming
elements like Cr, Molybdenum
This method is not good for powders of low carbon steels
 Reduction
 Reduction of compounds particularly oxides, by the use of reducing agents.
 Other compounds such as hydrides, oxalates and formats can also be
reduced.
 Widely used for producing powders of Iron, Copper, Nickel, Cobalt,
Tungsten, Molybdenum, Tantalum, Thorium and Titanium
 Gases such as hydrogen, carbon monoxide, disassociated ammonia, coal
gas, enriched furnace gas, natural gas, partially combusted hydrocarbons,
alkaline metal vapors are used as reducing agents.
 The reaction for reduction of metallic oxides for hydrogen or carbon
monoxide
MO + H2  M + H2O
MO + CO  M + CO2
 A typical example of solid state reduction is the production of sponge iron
powders.
 Sponge iron powders can be produced by two methods, Hoeganaes and
Pyron process
 Reduction
Hoeganaes Process:
 Pure magnetite (Fe3O4) is crushed and treated with coke and
limestone in silicon carbide containers at 12000C for 24 hours.
 Limestone acts as a flux and prevents Sulphur from contamination
of powders
 The spongy mass is then crushed to fine sizes.
 The fine size powder is reduced in a hydrogen atmosphere in a
mesh belt furnace.
Pyron Process:
 Mill scale is used as raw material.
 Involves the conversion of magnetite to hematite to facilitate
subsequent reduction by hydrogen.
 Reduction is carried out at a temperature of 9800C
 Electrolytic Deposition
Metal powders can be produced by electro deposition from aqueous solution and
fused salts.
This method is mainly used for producing copper, iron powders and also used for
producing zinc, tin, nickel, cadmium, antimony, silver, lead, beryllium powders.
Copper powder: Solution containing copper sulphate and sulphuric acid;
crude copper as anode
 Reactions:
 at anode: Cu  Cu+ + e
 at cathode: Cu+ + e-  Cu
Iron powder: Anode is low carbon steel; cathode is stainless steel. The
iron powder deposits are subsequently pulverized by milling in hammer
mill. The milled powders are annealed in hydrogen atmosphere to make
them soft.
Mg powder: Electrodeposition from a purified magnesium sulphate
electrolyte using insoluble lead anodes and stainless steel cathodes
 Electrolytic Deposition
 Powders of thorium, tantalum, vanadium: Fused salt electrolysis
is carried out at a temperature below melting point of the metal. Here
deposition will occur in the form of small crystals with dendritic shape.
 In this method, final deposition occurs in three ways,
 A hard brittle layer of pure metal which is subsequently milled to
obtain powder (eg. iron powder)
 A soft, spongy substance which is loosely adherent and easily
removed by scrubbing
 A direct powder deposit from the electrolyte that collects at the
bottom of the cell
 Factors promoting powder deposits are:
 high current density
 low metal concentration
 pH of the bath
 low temperature
 high viscosity
 circulation of electrolyte to avoid of convection
 Electrolytic Deposition

Advantages:
Powders of high purity with excellent sinterability
Wide range of powder quality can be produced by
altering bath composition

Disadvantages:
Time consuming process; Pollution of work place
because of toxic chemicals;
Waste disposal is another issue;
Cost involved in oxidation of powders and hence they
should be washed thoroughly
 Compaction of metal powders
 Compaction is enables the forming of loose metal powders into required
shapes with sufficient strength to withstand till sintering is completed.
 Compaction is done without the application of heat in most of the processes.
 Powder compaction techniques can be classified
Methods without application of pressure
 Loose powder compaction in mould
 Vibratory compaction
 Slip casting
 Slurry casting
Methods with applied pressure
 Cold die compaction
 Isostatic pressing
 Powder rolling
 Powder extrusion
 Explosive compaction
 Compaction - Pressure less compaction techniques
No external pressure is involved
Loose powder sintering:
 Also known as loose powder shaping, gravity sintering,
pressure less sintering.
 The metal powder is vibrated mechanically into the mould,
which is the negative impression of the product and heated to
sintering temperature.
 This is the simplest method and involve low cost equipment.
 The main reasons for not using this method for part
production are, difficulty of part removal from the mould
after sintering and considerable shrinkage during sintering.
 Compaction - Pressure less compaction techniques
Slip casting: Used for compacting metal and ceramic powders to
make large and complex shapes for limited production runs
A slip is a suspension of metal or ceramic powder in water or other
soluble liquid which is pored into a mould, dried and further sintered.
Steps in slip casting:
 Preparing assembled plaster mould
 Filling the mould
 Absorption of water from the slip into the porous mould
 Removal of part from the mould
 Trimming of finished parts from the mould
 Compaction of metal powders
Slurry casting:
 This process is similar to slip casting.
 Except that a slurry of metal powders with suitable
liquids, various additives, and binders is poured into a
mould and dried.
 The solvent is removed either by absorption into the
Plaster of Paris or by evaporation.
 Very high porous sheet for use as electrodes in fuel cells
and nickel- cadmium rechargeable batteries are produced
by this method.
 Compaction of metal powders
Advantages of slip casting:
 Products that can not be produced by pressing
operation can be made
 No expensive equipment is required
 Works best with finest powder particles
Disadvantage:
 Slow process
 Limited commercial applications
Applications: Tubes, boats, crucibles, cones,
turbine blades, rocket guidance fins; Also products
with excellent surface finish like basins, water
closets.
 Compaction of metal powders
Pressure compaction techniques
These techniques involve application of external pressure to compact the loose powder
particles
Die compaction: Loose powder is shaped in a die using a mechanical or hydraulic press
giving rise to densification.
Unidirectional and bidirectional compaction involves same number of stages
They are, i) charging the powder mix, ii) applying load using a punch, iii) removal of load
by retracting the punch, iv) Ejection of green compact.
 Cold Isostatic Pressing
 CIP is a compaction process in which isostatic fluid pressure is applied to a powder mass
at room temperature to compact it into desired shape.
 Water or oil can be used as pressuring medium.
 Process details: High density near-net shape green parts, long thin walled cylinders, parts
with undercuts can be readily fabricated.
 In this process, pressure is applied simultaneously and equally in all directions using a
fluid to an elastomeric fluid with powder at room temperature.
 Sintered CIP component can reach up to 97 % of theoretical density.
 Steps in this process is shown in flowchart.
 Good mould filling is required in CIP because the initial powder distribution and density
affect the preform shape.
 Powder size, shape, density and mechanical properties affect the flowability of powder
into the mould and the packing density.
 Optimum pressing is obtained by using a free-flowing powder along with controlled
vibration or mould tapping.
 Materials used for flexible moulds are natural, synthetic rubber like neoprene, urethane,
nitrile, silicones.
 Cold Isostatic Pressing
 During pressing, high density is achieved at a low pressure, while the green strength of
the compact rises linearly with pressure.
 The pressure applied can range from 100- 400 MPa. Initially the applied stress serves to
improve the density of the compact by particle sliding and rotation.
 In the next stage, deformation of powder particles occur and particle characteristics like
shape play vital role in deciding this stage.
 Irregular particles which interlock with one another and also deform during both the
stages, tend to densify much easily than spherical powders.
 In the case of spherical powders, in spite of their higher initial packing densities, particles
do not mechanically interlock with one another and hence do not easily deform. Hence
high pressures are required for their compaction.
 Cold Isostatic Pressing
Advantages of CIP:
Uniform, controlled, reproducible densification of powder
long, slender parts can be pressed
Near net shape forming
Short production times
Economy of operation for complex and large parts.
Applications:
Metallic filters made from bronze, brass, stainless steel,
Inconel, Monel, Titanium,
high speed tools, carbide tools.
Also ceramic parts such as sparks plugs and insulators are
made by this method.
 Hot Isostatic Pressing
 Ideal method for consolidation of powders of nickel and cobalt
base super alloys, tool steels, maraging steels, titanium alloys,
refractory metal powders, cermets.
 It has got variety of applications including bonding of dissimilar
materials, consolidation of plasma coatings, processing hard and
soft magnetic materials etc.
 HIP is the application of pressure at elevated temperatures to
obtain net or near net shape parts from metal, ceramic, cermet
powders.
 HIP unit consists of a pressure vessel, high temperature furnace,
pressurizing system, controls and auxiliary systems (material
handling, vacuum pumps, metering pumps).
 The pressure vessel is made of low alloy steel. Its function is to
heat the powders while applying uniform gas pressure on all the
sides.
 Furnaces are of radiation or convection type heating furnaces with
graphite or molybdenum heating elements. Nichrome is also used.
 Hot Isostatic Pressing
 The furnace heats the powder part, while pressurizing medium (a gas) is used
to apply a high pressure during the process.
 Generally, argon, nitrogen, helium or even air is used as pressurizing medium.
 The pressurizing gas, usually argon, is let into the vessel and then a
compressor is used to increase the pressure to the desired level.
 The furnace is then started and both temperature and pressure are increased to
a required value.
 HIP presses are available in diameters up to 2m with pressures ranges from 40
to 300 MPa with temperature range from 500 to 2200 °C.
 The processing time can last up to 4 hours depending on the material and size
of the part.
 During HIP, the pores are closed by flow of matter by diffusion and creep, but
also bonded across the interface to form a continuous material.
 Commonly used heating elements: Kanthal heating element – up to 1200 °C;
 Molybdenum heating element – 1200 to 1700 °C; Graphite heating element –
2000 to 2600 °C.
Hot Isostatic Pressing
 Sintering
It is the process of consolidating either loose aggregate of powder or a green
compact of the desired composition under controlled conditions of temperature and
time.
Sintering is a thermal treatment carried out at temperatures below the
melting point of main constituent i.e., 0.7 – 0.9 of Tm (Tm is Melting point).
Types of sintering:
a) Solid state sintering – Densification occurs mainly because of atomic
diffusion in solid state.
b) Liquid phase sintering – The densification is improved by employing a
small amount of liquid phase (1-10% vol). Sufficient amount of liquid is
formed between the solid particles of the compact sample.
c) Activated sintering – An alloying element called ‘doping’ is added in small
amount improves the densification. Ex. Doping of nickel in tungsten
compacts
d) Reaction sintering – Reaction sintering occurs when two or more
components reacts chemically during sintering to create final part.
e) Ex. reaction between alumina and titania to form aluminium titanate at
1553 K.
 Sintering
Sintering theory:
 First theory was proposed by Sauerwald in 1922. This theory says that two
stages are involved in sintering namely adhesion and recrystallization.
 Adhesion occurs during heating due to atomic attraction.
 Recrystallization occurs at temperatures above 0.7 of Tm, consists of diffusion
of atoms between adjacent grains.
 In recrystallisation, microstructure changes, phase changes, grain growth,
shrinkage occurs.
Solid state sintering process
 Solid state sintering is carried out at temperatures where material transport due
to diffusion is appreciable. Surface diffusion is not sufficient, atomic diffusion is
required.
 This occurs by replacing high energy solid-vapour interfaces (with free energy
γSV) with the low energy solid-solid interface (particle-particle) of free energy
γSS. This reduction in surface energy causes densification.
 Sintering
Stages in solid state sintering
 In general, solid state sintering can be divided into three stages
 1st stage: Necks are formed at the contact points between the particles, which continue to
grow. During this rapid neck growth takes place. Also the pores are interconnected and
the pore shapes are irregular.
 2nd stage: In this stage, with sufficient neck growth, the pore channels become more
cylindrical in nature. The curvature gradient is high for small neck size leading to faster
sintering.
 3rd or final stage: In this stage, pore channel closure occurs and the pores become
isolated and no longer interconnected. Porosity does not change and small pores remain
even after long sintering times
 Secondary Operations
 Sizing: Post sintering operation used to correct size, warping,
distortion and other dimensional defects during sintering and also
used to improve wear properties.
 Coining: Carried out after sintering achieves the same results as
the sizing operation. Significant improvement in hardness, density
and strength.
 Machining: Machining is done to the P/M products after sintering
to holes, threads, undercuts, grooves for complex designs.
 Heat treatment: Used to relieve internal stresses formed during
sintering and to improve hardness and strength for P/M products.
 Repressing: Primary aim of repressing is densification of the
sintered part to give improved physical mechanical properties.
 Steam Treatment: Exposing the part to a temperature around 5500C
to high pressure steam. To improve corrosion resistance
 Infiltration:
 Impregnation:
 Joining:
 Plating: