Al-MnO2 system

Powder production

Analysis of powder

1. Sieve analysis

2. TG-DTA analysis

Blending

Mixing

Pressing

Sintering

Microstructural observation

Electrical Conductivity measurement

To study the effect of addition of Mno2 into Al powder

Elemental or alloy powder Additives (die lubricants)

Mixing or blending

Compaction

Sintering

Repressing

Finished product
Powder Metallurgy →

the name given to the process by which fine powdered materials are
blended, pressed into a desired shape (compacted), and then heated
(sintered) in
a controlled atmosphere to bond the contacting surfaces of the particles and
establish the desired properties.

→ it is commonly designated as P/M

→ it readily lends itself to the mass production of small, intricate parts of high
precision, often eliminating the need for additional machining or finishing.

→ has a little material waste; unusual materials or mixtures can be utilized;

and
controlled degrees of porosity or permeability can be produce.

♥ Major areas of application tend to be those for which the P/M process has
strong economical advantage or where the desired properties and
characteristics would be difficult to obtain byany other method.

Background/history :

• Early 3000 B.C. – a crude form of powder metallurgy appears to have

existed
in Egypt

• Mid- or Late 19th Century – the mass production of P/M products begin

• Early 20th Century – powder metallurgy was used to produce copper coins
and
medallions, platinum ingots, and tungsten wires, the primary material for
light
bulb filaments

• 1920s – tungsten carbide cutting-tool tips and nonferrous bushings were

produced. Other early products were self-lubricating bearings and metallic
filters

• After World War II – a period of rapid technological development

occurred
which are based primarily on automotive applications, and iron and steel
replaced copper as the dominant P/M material.
– aerospace and nuclear developments created accelerated demand for
refractory and reactive materials, where P/M processing is quite attractive.
• 1960s – full-density products emerged.

• 1970s – high-performance superalloy components, such as aircraft turbine

engine parts

• 1980s – the commercialization of rapidly–solidified and amorphous

powders
and the development of P/M injection molding technology

Recent years have been ones rapid development and growth for the
P/M industry:
From 1960-1980 – the consumption of iron powder increased tenfold
From 1980-1990 – the similar increase as the past years occurred and this
exponential growth continues

♥ P/M has become a proven method of parts production and is now

considered as an
alternative in the manufacture of many components.
♥ The automotive applications account for nearly 75% of the powder
metallurgy market.

Other Areas where Powder Metallurgy Products are used

extensively:
• Household appliances
• Recreational equipment
• Hand tools
• Hardware items
• Business machines
• Industrial motors
• Hydraulics

Areas of Rapid Growth :

• Aerospace applications
• Advanced composites
• Electronic components
• Magnetic materials
• Metalworking tools
• A variety of biomedical and dental applications

High-volume Materials :
• Stainless steel
• High-strength and high-alloy steels
• Aluminum
• Aluminum alloys
• Iron
• Copper
ALUMINUM POWDERS and ALUMINUM ALLOYS

• They are produced almost exclusively by gas atomization.

• For most applications, the atomizing gas is compressed air; however, in some special cases, inert
gases (helium, nitrogen, and argon) are used.
• Atomized aluminum powders are used in a variety of applications that include pyrotechnics,
explosives, rocket fuel, termite welding, aluminothermic reduction, chemical processes (as
catalyst or reagent), additives for lightweight concrete, pharmaceuticals, and pigments for paints
and printing inks.
• With few exceptions, the demand is for unalloyed powder of various standards of purity.

• Aluminum alloy P/M, historically a small percentage (about 1%) of the total powder market, has
been enjoying a revival in recent years in automotive applications because of the need to reduce
weight, lower emissions, and boost fuel economy.

Gas Atomization
Gas atomization is the process where the liquid metal is disrupted by a high-velocity gas such as
air,nitrogen, argon, orhelium. Atomization occurs by kinetic energy transfer from the atomizing medium
to the metal.
Gas atomization differs from water atomization in many respects.
Rather than being dominated by the pressure of themedium like water atomization, it is found that the
gas-to-metal ratio is the dominant factor in controlling particle size,with median particle size being related
inversely to the square root of the gas-to-metal ratio.
Fig. Two-fluid atomization with (a) free-fall design (gas or water) and (b) continued nozzle
design (gasonly). Design characteristics: , angle formed by free-falling molten metal and
atomizing medium; A, distancebetween molten metal and nozzle; D, diameter of confined molten
metal nozzle; P, protrusion length of metalnozzle

BLENDING OF POWDERS

• It is defined as the thorough intermingling of powders of the same nominal composition.

• The implication with blending is that the constituents in the vessel are virtually identical except
for some minor physical Characteristics.
• For example, one may be interested in blending several lots of powder that have slight variations
in moisture or color.
• Premixing is the preparation of a uniform mixture of two or more components.
• The implication with mixing is that the constituents in the vessel are different.
• They may differ in chemical composition or may be physically dissimilar.
• Many properties of powders and sintered parts--such as powder flow, apparent density, ejection
stress, delubrication behavior, dimensional change, and mechanical strength--are quite sensitive
to even small changes in particle size distribution and to fluctuations in the concentrations of
components within a powder mixture.
• In many cases, the P/M parts producer is interested in relatively large uniformly blended powder
lots, because costly and time-consuming process adjustments, often of an empirical nature, must
be made.
• Adjustments are often made from lot to lot, even when the various lots are within given
specifications.

Equipment for Blending and Premixing

 • Many different types of machines are available for blending and premixing solids. The high
density, abrasive nature,
• frictional characteristics, and tendency to segregate of metal powders, however, reduce the
suitability of some machines.
• A blender suitable for metal powders should:
• Achieve a maximum blending in minimum time
• Have a gentle mixing action to avoid particle degradation
• Provide repeatability of blending
• Provide for complete batch discharge
• Provide accessibility for ease of cleaning
• Have low power consumption
• Require low maintenance
• Provide dust-tight operation

MILLING

MILLING OF MATERIALS,

Whether hard and brittle or soft and ductile, is of prime interest and of economicimportance to the P/M
industry.
Mechanical comminution is the most widely used method of powder production for hardmetals and oxide
powders.
Secondary milling of spongy cakes of oxide-reduced, atomized, or electrolytic powders is themost
common milling process; hammer and rod mills are used for this type of milling.
Depending on the degree to whichthe material is sintered, either primary particle size distribution is
reestablished during milling or larger agglomerates areproduced.Mechanical comminution is restricted to
relatively hard, brittle metals (electrolytic iron or bismuth, for example), somereactive metals such as
beryllium and metal hydrides, ductile metals used for producing metal flakes, and chemicallyembrittled
materials such as sensitized stainless steel.
Increasing interest in metal powder with particle sizes that are finer than the particle sizes of powders
produced byatomization has reactivated interest in milling, particularly in solid-state alloying or high-
energy milling.
However,milling of metal powders has received minimal attention to date. Research conducted on ball
milling of metals isprimarily proprietary and empirical, and thus restricted to specialized P/M
applications.
Objectives of milling include:
• Particle size reduction (comminution or grinding)
• Particle size growth
• Shape change (flaking)
• Agglomeration
• Solid-state alloying (mechanical alloying)
• Solid-state blending (incomplete alloying)
• Modifying, changing, or altering properties of a material (density, flowability, or work
hardening)
• Mixing or blending of two or more materials or mixed phases
• Nonequilibrium processing of

Mechanism of milling:

Changes in the morphology of powder particles during milling results in the following events.

1. Microforging,
2. Fracture,
3. Agglomeration,
4. Deagglomeration

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 or vande Waals

forces

Deagglomeration => Breaking of agglomerates

The different powder characteristics influenced by milling are shape, size, texture,
particle size distribution, crystalline size, chemical composition, hardness, density,
flowability, compressibility, sinterability, sintered density

Milling equipment: The equipments 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

Grinding: Different types of grinding equipments/methods are shown in the figure

Ball mills

• This contains cylindrical vessel rotating horizontallyalong the axis. Length of the cylinder is more or
less equal to diameter. The vessel is charged with the grindingmedia. The grinding media may be made of
hardenedsteel, or tungsten carbide, ceramics like agate, porcelain, alumina, zirconia. During rolling of
vessel, the grindingmedia & powder particles roll from some height. Thisprocess grinds the powder
materials by impact/collision &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 agentsuch as water, alcohol or hexane is employed.

• Optimum diameter of the mill for grinding powders isabout 250 mm

COMPACTION

Pressure compaction techniques

• These techniques involve application of external pressure to compact the loose powder particles;
Pressure applied can be unidirectional, bidirectional or hydrostatic in
nature.

• Die compaction: In this process, loose powder is shaped in a die using a mechanicalor hydraulic press
giving rise to densification. The mechanisms of densification dependon the material and structural
characteristics of powder particles.

• Unidirectional and bidirectional compaction involves same number of stages and aredescribed in this
figure. They are, i) charging the powder mix, ii) applying load using apunch (uni-) or double punch (bi-)
to compact powders, iii) removal of load byretracting the punch, iv) ejection of green compact.

Effect of powder characteristics

For a good compaction, 1) irregular shaped particles are preferred as they give better
interlocking and hence high green strength, 2) apparent density of powders decides the die
fill during compaction. Hence powder size, shape & density affect the apparent density, 3)
flow rate affects the die fill time, and once again powder size, shape & density affect the
flow rate.

Powder behavior during compaction

- Compaction involves,
1) flow of powder particles past one another interacting with eachother and with die-punch,
2) deformation of particles. In the case of homogeneouscompaction, two stages are observed.

First stage =>

rapid densification occurs when pressure is applied due to particle movement and rearrangement resulting
in improvedpacking;

Second stage =>

increase in applied pressure leads to elastic and plasticdeformation resulting in locking and cold welding
of particles. In the second stage, largeincrements in pressures are seen to effect a small increase in
density.

• The green compact produced can be considered as a two-phase aggregate consisting of

powder particles and porosity each having own shape and size.

• Compaction can be done at low and high temperatures. Room temperature compaction
employs pressures in the range of 100-700 MPa and produce density in the range of 60-
90% of the theoretical density. At higher temperatures, pressures are kept low within the
limits for preventing die damage.

• In single die compaction, powders close to the punch and die walls experience much
better force than in center. This results in green density variation across the sample
length. Longer the sample more the density difference. This non-uniformity can result in
non-uniformity in properties of sintered part.
• This density variation and hence final property variation can be greatly reduced by
having double ended die compaction. In this case, powder experiences more uniform
pressure from both top and bottom, resulting in minimization of density variation. But
this variation will still be considerable if the components have high aspect ratio (length
to diameter ratio). This means that long rods and tubes cannot be produced by die
compaction. In this case, isostatic pressing can be used.

Schematic of powder compaction

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.
• Types of sintering:

a) solid state sintering – This is thecommonly occurringconsolidation of metal and alloy powders. In this,
densification occurs mainly becauseof atomic diffusion in solid state.

b) Liquid phase sintering – The densification in improved by employing a small amountof liquid phase
(1-10% vol). The liquid phase existing within the powders at thesintering temperature has some solubility
for the solid. Sufficient amount of liquid isformed between the solid particles of the compact sample.
During sintering, the liquidphase crystallizes at the grain boundaries binding the grains. During this stage,
there is arapid rearrangement of solid particles leading to density increase. In later stage, solidphase
sintering occurs resulting in grain coarsening and densification rate slows down.Used for sintering of
systems like tungsten-copper and copper-tin. Also covalentcompounds like silicon nitride, silicon carbide
can be made, that are difficult to sinter.

c) Activated sintering – IN this, an alloying element called ‘doping’ is added in smallamount improves
the densification by as much as 100 times than undoped compactsamples. Example is the doping of nickel
in tungsten compacts

d) Reaction sintering –
IN this process, high temperature materials resulting from chemicalreaction between the individual
constituents, giving very good bonding. Reaction sinteringoccurs when two or more components reacts
chemically during sintering to create final part.A typical example is the reaction between alumina and
titania to form aluminium titanate at1553 K which then sinters to form a densified product.

Sintering theory
- Sintering may involve,

1) single component system – here self-diffusion is the major material transport mechanism and the
driving force resulting from a chemical potentialgradient due to surface tension and capillary forces
between particles,
2) multi-componentsystem (involve more than one phase) – inter-diffusion occurs with the concentration
gradient being the major driving force for sintering in addition to self-diffusion caused bysurface tension
and capillary forces. IN this sintering, liquid phase formation and solidsolution formation also occurs with
densification.

- First theory was proposed by Sauerwald in 1922. This theory says that two stages areinvolved in
sintering namely adhesion and recrystallisation.
Adhesion occurs during heatingdue to atomic attraction and recrystallisation occurs at recrystallisation
temperature (above0.5 Tm).
In recrystallisation, microstructure changes, phase changes, grain growth, shrinkageoccurs.