Introduction:-

Powder metallurgy is the process of blending fine powdered materials, compacting

the same into a desired shape or form inside a mould followed by heating of the
compacted powder in a controlled atmosphere, referred to as sintering to facilitate the
formation of bonding of the powder particles to form the final part.

Thus, the powder metallurgy process generally consists of four basic steps :(1) powder
manufacture, (2) blending of powders, (3) compacting of powders in a mould or die,
and(4) sintering. Compacting is generally performed at room temperature and at high
pressure. Sintering is usually done at elevated temperature and at atmospheric
pressure. Often, compacting and sintering are combined. Optional secondary
processing often follows to obtain special properties or enhanced dimensional precision.
Powder Metallurgy route is very suitable for parts that are required to be manufactured
from a single or multiple materials (in powder form) with very high strength and melting
temperature that pose challenge for the application of casting or deformation processes.
2.Objectives of sintering :
1-the principal goal of sintering is the reduction of compact porosity .

2-increase of inter particle contact area with time .

3-rounding-off of sharp angles and points of contact .

4-decrease in volume of interconnected pores .

5-continuing isolation of pores .

6-grain growth and decrease in volume of isolated pores.

Sintering:-
Sintering is a manufacturing process in which a fine powder that has been formed into a
shape is subsequently fired at temperature below melting point. The compact, when
fired, densifies and becomes non-porous. The powder particles form bonds at this
temperatures and the contact points between particles, which were originally formed
under the mechanical pressure during compaction, increase in size and strength,
improving mechanical properties. sintering is a thermal treatment that densification
accompanies it.

Densification almost always requires shrinkage. The shrinkage takes place as a result
of materials being transported by one or more of several diffusion processes. This may
involve a liquid or reactive liquid or diffusion at grain boundaries or through the volume
of particle. Therefore, it is a densification process where porosity is usually reduced and
the grain size increases significantly through mass transport. This is important because
it allows an engineer to form a dense ceramic body at temperatures below the often
very high melting temperature of the ceramic. For many properties such as strength,
thermal conductivity, and translucency, in order to reach a maximum value for a
product, it is necessary to remove as much porosity as possible. A formed powder
compact can be anywhere from 40% to 75% dense, with little strength. A sintered body
can have much higher strengths and densities exceeding 99%.

The ability to achieve dimensional tolerances in powder metallurgy parts arises directly
from the control of the sintering process and in particular shrinkage. Thus a detailed
understanding of the sintering process and the associated shrinkage is of considerable
importance.

Sintering is the process of compacting and forming a solid mass of material by heat or
pressure without melting it to the point of liquefaction. Sintering happens naturally in
mineral deposits or as a manufacturing process used with metals, ceramics, plastics,
and other materials.

Sintering is the process of heating the powder compacts in a furnace to a temperature

close to the melting point of at least one of the major constituents in a controlled
atmosphere.
It may also carry out under protective gas normally hydrogen or in a vacuum if the
material tends to react with the protective gas. The heating causes the metal particles to
sinter i.e cement the particles together in a cellular structure.

Sintering is performed to get final strength and hardness required in a finished product.
The important governing variables of Sintering are temperature, time and sintering
atmosphere. During sintering workpiece may changes. It may expand or contract.
Bronze tends to expand and iron and brass tend to contract.

 Types of sintering:

a) solid state sintering – This is the commonly occurring consolidation of metal and
alloy powders. In this, densification occurs mainly because of atomic diffusion in solid
state.
For a different structure of atoms in a lattice, such as anionic and metallic bonding
in cermets (metal-oxide), the boundary strength is defined by van der Waals or
adhesion forces. The arrangement of atoms on the phase boundary can be
accelerated by dissolving procedures occurring simultaneously, which makes
sintering easier.

The actual compaction can occur through partial, rather complicated processes.
At a noticeable difference in partial diffusion coefficients, such as in Cu-Ni system,
it may be possible, that diffusion pores sometimes originate in a phase with a
higher diffusion coefficient (Cu) (Kirkendall phenomenon) and particles in a phase
with a lower diffusion coefficient (Ni) exhibit an increase in volume. Aside from
the volume diffusion, the flow of the material which is needed for the material
homogenization can occur through the surface diffusion. In Fig. 10 , origination of
a pore in Cu-Zn system as a result of the Kirkendall phenomenon is shown, where
Zn to Cu diffusion rate is higher than the diffusion rate of Cu to a newly
originating phase (brass).

Other complications for the sintering process can emerge in components having
substantially different heterogeneous diffusion coefficients (AB) in comparison
with autodiffusion coefficients (AA, BB), leading also to a different growth
rate of a contact (neck) AB than in a case of AA or BB. As a result, stresses
inducing plastic deformation or leading to a separation of individual particles can
occur.

Fig. 10 Kirkendall phenomenon in Cu-Zn system [7].

b) Liquid phase sintering – The densification in improved by employing a small

amount of liquid phase (1-10% vol). The liquid phase existing within the powders at the
sintering temperature has some solubility for the solid. Sufficient amount of liquid is
formed between the solid particles of the compact sample. During sintering, the liquid
phase crystallizes at the grain boundaries binding the grains. During this stage, there is
a rapid rearrangement of solid particles leading to density increase. In later stage, solid
phase sintering occurs resulting in grain coarsening and densification rate slows down.
Used for sintering of systems like tungsten-copper and copper-tin. Also covalent
compounds like silicon nitride, silicon carbide can be made, that are difficult to sinter.
The sintering process is affected by a liquid phase in a way and extent which
depends on an amount and time of origination of the melt. If no mean
equilibrium concentration of a sintered alloy occurred during the isothermal
sintering, in which a solid and liquid phase was in equilibrium, an occurrence of a
melt is a transient phenomenon (a tendency to achieve the equilibrium state).
Wettability of a solid phase by a liquid phase has a crucial significance for the
sintered alloy quality (Fig.11). For a liquid to wet a solid, the following relation
applies for a change in the specific surface energy (according to Dupré):

 = SV +( LV - SL)

where γSV – surface stress between a solid and vapour phase; γLV – surface stress
between a liquid and vapour phase; γSL – surface stress between a solid and liquid
phase.

Fig. 11. Wetting angle definition[8].

For a contact between S-L to originate,  must be positive, that means SL < S
+ L. According to Young-Dupré, wettability can be expressed by a value of a
wetting angle :

Through a combination of the above mentioned equations, we obtain a relation

enabling to assess the effect of a wetting angle on a change in the sintered
material resulting structure:

 = LV (1 + cos )
The lower the  magnitude and surface stress on the interfacial area, the higher
the energy increase. Wettability can be positively influenced by alloying elements
without affecting other properties of the sintered material. It is important for
sintering in the presence of a liquid phase, that wettability of a solid phase by a
liquid is as high as possible, i.e.   0°

Fig. 12 The melt well wetting a solid (a) and not wetting a solid surface (b) [9].

If the wettability angle  exceeds a defined value (Fig.12 ), a melt cannot

penetrate between powder particles and becomes isolated. Solid particles form a
solid skeleton in which the melt is roughly distributed. This reduces the melt
effect on compaction and in the end leads to sintered products not meeting
demanded requirements.

c) Activated sintering – In this, an alloying element called ‘doping’ is added in small

amount improves the densification by as much as 100 times than undoped compact
samples. Example is the doping of nickel in tungsten compacts

d) Reaction sintering – IN this process, high temperature materials resulting from

chemical reaction between the individual constituents, giving very good bonding.
Reaction sintering occurs 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 aluminum titanate at 1553 K which then sinters to form a densified
product.
Other than mentioned above, rate controlled sintering, microwave sintering, gas plasma
sintering, spark plasma sintering are also developed and practiced.

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 potential gradient due to
surface tension and capillary forces between particles,

2) multi-component system (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 by surface tension and capillary forces. In this sintering, liquid
phase formation and solid solution formation also occurs with densification.

- First theory was proposed by Sauerwald in 1922. This theory says that two stages are
involved in sintering namely adhesion and recrystallisation. Adhesion occurs during
heating due to atomic attraction and recrystallisation occurs at recrystallisation
temperature (above 0.5 Tm). In recrystallisation, microstructure changes, phase
changes, grain growth, shrinkage occurs.
Factors influencing sintering of one-component systems are divided to:

A. Primary factors
1) Total actual contacting area.
2) Free surface energy of all surfaces including pores.
3) Mutual orientation of contacting areas.
4) Diffusion coefficients (lattices, boundaries of grains and surfaces).
5) Critical shear stress (at participation of plastic flow).
6) Vapour pressure and evaporation velocity (at participation of evaporation and
condensation).
7) Crystalline structure and a type of bonding.
B. Secondary factors

1) Surface activity (actual surface structure).

2) Lattice activity (cold forming, internal stress, lattice imprefections induced by
a manufacturing operation).
3) Allotropic modification.
Foreign materials: a) soluble b) insoluble c) surface layers (e.g. oxide layers) d) gas
(adsorbed by effect of a sintering atmosphere etc.)

Solid State Sintering Process:-

Condition for sintering:
1) Densification occurs during sintering and 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.
2) 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.
3) Initially free energy of solid-solid interface must be lower than free energy of solid
vapour interface. The process of sintering will stop if the overall change in free
energy of the system (dE) becomes zero, i.e.,

Where dASS & dASV are the interfacial area of solid-solid and solid-vapour
interfaces.
4) Initially, the surface area of compact represents the free surface area, since no grain
boundaries have developed and hence:

.
As sintering proceeds, ASV decreases and ASS increases. The sintering process will
stop when dE = 0,

5)
Densification stops when - dASV / dASS is close to zero. To achieve densification without
grain growth, the solid-solid interface must be maximized. Such conditions can be
achieved by doping or by using suitable sintering conditions for surface free energy
maximization.

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. With sufficient time at the sintering temperature, the
pore eventually becomes rounded. As the neck grows, the curvature gradient
decreases and sintering also decreases. This means there is no change in pore
volume but with change in pore shape  pores may become spherical and
isolated. With continued sintering, a network of pores and a skeleton of solid
particle is formed. The pores continue to form a connected phase throughout the
compact.

 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.

Driving force for sintering

  The main driving force is excess surface free energy in solid state sintering. The
surface energy can be reduced by transporting material from different areas by
various material transport mechanisms so as to eliminate pores.
 Material transport during solid state sintering occurs mainly by surface transport,
grain boundary transportation. This surface transport can be through adhesion,
surface diffusion. Many models available to describe sintering process – like
viscous flow, plastic flow, grain boundary and volume diffusion models. These
models will be briefly described here.

Mechanism in solid state sintering

As discussed earlier, material or atom transport forms the basic mechanism for
sintering process. A number of mechanisms have been proposed for sintering
operation. These are,
1. Evaporation condensation,
2. diffusion (can be volume diffusion, grain boundary diffusion, surface diffusion),
3. viscous flow,
4. plastic flow
1. Evaporation and condensation mechanism
The basic principle of the mechanism is that the equilibrium vapor pressure over a
concave surface (like neck) is lower compared to a convex surface (like particle
surface). This creates the vapor pressure gradient between the neck region and
particle surface. Hence mass transport occurs because of vapor pressure gradient
from neck (concave surface) to particle surface (convex surface). The driving force
of this is based on Gibbs-Thomson equation,

where T and To are chemical potentials of initial and final surfaces, R is universal
gas constant, T is temperature in K, p and po are partial pressures over the
curved and flat surface respectively,  is the surface free energy,  is the
atomic volume
2. Diffusion mechanism
- Diffusion occurs because of vacancy concentration gradient. In the case of two
spheres in contact with each other, a vacancy gradient is generated between the two
surfaces. This condition can be given by,

Where C and Co are the vacancy concentration gradient around the curved and flat
surface.
- Kuczynski has derived empirical relation for neck growth rate for the following two
cases, i) a sphere in contact with flat surface – the rate of neck growth is
proportional to seventh root of time (t1/7),

ii) when two spheres are in contact – the neck growth rate is, x5/a2 = 40 
D.t /RT where a – radius of sphere, D – volume diffusivity of material,  –
atomic or molecular volume.
- Neck growth due to surface diffusion, lattice diffusion, vapour transport, grain
boundary transport from GB source, lattice diffusion from sources on GB, lattice
diffusion from dislocation sources

3. Viscous flow mechanism

According to this concept, sintering occurs due to the presence of lattice vacancies.
This is important in sintering of glass. Frenkel developed the equation, (x2/a) = 3/2

(/η).t where x is the neck radius & a is the radius of particle. Increasing the
temperature results in increased plasticity of metal powders. Balshin proposed the
following mechanisms to happen during sintering.

1. Particle rearrangement,
2. particle shape change,
3. grain growth.

Frenkel suggested that surface tension lead to sintering and solids could behave like
newtonian liquids at high temperatures i.e., sintering occurs by viscous flow. He derived
an equation for the viscosity coefficient, η = kT/D where k is the Boltszman’s

constant, T is the absolute temperature, D is the self-diffusion coefficient,  is the

atomic volume. He derived an expression on neck growth during sintering of two
spherical particles of radius a with time t as, x2 = 3a /2η where x is the neck radius

and  is the surface energy.

4. Plastic flow mechanism

Bulk flow of material by movement of dislocations has been proposed as possible

mechanism for densification during sintering. Importance was given to identify
dislocation sources during the sintering process. Even if frank read sources are present
in the neck region, the stress available for dislocation generation is very small,
indicating that the generation of dislocation must come from free surfaces.
Only if the surface is very small of the order of 40 nm, the stress required for dislocation
generation will be sufficient. But experimental results have shown the absence of
applied stress and plastic flow is expected to occur during early stages of sintering.
Plastic flow mechanism is predominant during hot pressing.
Property changes during sintering:-

 Densification is proportional to the shrinkage or the amount of pores removed in

the case of single component system
 In multicomponent system, expansion rather than shrinkage will result in
densification and hence densification cannot be treated as equal to the amount of
porosity removed.
 densification results in mechanical property change like hardness, strength,
toughness, physical properties like electrical, thermal conductivity, magnetic
properties etc. Also, change in composition is expected due to the formation of
solid solution.

Mechanism during liquid phase sintering:-

In the sintering of multi-component systems, the material transport mechanisms involve

self-diffusion and interdiffusion of components to one another through vacancy
movement. Sintering of such systems may also involve liquid phase formation, if the
powder aggregate consists of a low melting component whose melting point is below
the sintering temperature

Liquid phase sintering: In this, the liquid phase formed during sintering aids in
densification of the compacts. Liquid phase sintering employs a small amount of a
second constituent having relatively low melting point. This liquid phase helps to bind
the solid particles together and also aids in densification of the compact. This process is
widely used for ceramics – porcelain, refractories.

Three main considerations are necessary for this process to occurs,

1. Presence of appreciable amount of liquid phase,
2. Appreciable solubility of solid in liquid,
3. Complete wetting of the solid by liquid.

Three main stages are observed in liquid phase sintering,

1. Initial particle rearrangement occurs once the liquid phase is formed. The solid
particles flow under the influence of surface tension forces,
2. Solution & reprecipitation process: in this stage, smaller particles dissolve from
areas where they are in contact. This causes the particle centers to come closer
causing densification. The dissolved material is carried away from the contact
area and reprecipitate on larger particles,
3. solid state sintering
This form of liquid phase sintering has been used for W-Ni-Fe, W-Mo-Ni-Fe, W-Cu
systems. The three-stage densification is schematically shown in figure.

In solid phase sintering, the solid particles are coated by the liquid in the initial stage. In
liquid phase sintering, the grains are separated by a liquid film. The dihedral angle (θ) is
important. For the figure shown here, the surface energy for the solid-liquid-vapour-
system is, where s-s & l-s are the interfacial energies between two

solid particles and liquid-solid interfaces respectively.

For complete wetting θ should be zero. This means that two liquid-solid interface can be
maintained at low energy than a single solid-solid interface. This pressure gradient will
make the particles to come closer. If θ is positive, grain boundaries may appear
between the particles and an aggregate of two or more grains will be established. This
creates formation of rigid skeleton and will hinder with densification.

Sintering atmosphere
Functions of sintering atmosphere:
1. Preventing undesirable reactions during sintering,
2. Facilitate reduction of surface oxides,
3. Facilitating the addition of other sintering and alloying elements which enhance the
sintering rate and promote densification,
4. Aiding the removal of lubricants,
5. Composition control and adjusting the impurity levels.

The sintering atmosphere.:-

The main purpose of sintering atmospheres is to protect the powder compacts from
oxidation during sintering and to reduce residual surface oxides in order to improve the
metallic contact between adjacent powder particles. A further purpose of sintering
atmospheres is to protect carbon-containing compacts from decarbonization.

General problematic
Mainly three different types of sintering atmospheres are common in iron powder
metallurgy: reducing-decarbonizing (e.g. hydrogen, cracked ammonia), reducing-
carbonizing (e.g. endogas) and neutral (e.g. nitrogen). At a cursory glance, the choice
may seem obvious: A reducing atmosphere for carbon-free materials and a non-
decarbonizing or neutral atmosphere for carbon-containing materials. However, apart
from economical considerations, there are some technical and thermodynamical
problems which complicate both, the choice and the control of the proper atmosphere:

• Technical problems arise in connection with the proper control of flow rates and flow
directions of the atmosphere in continuous sintering furnaces. A continuous furnace of
modern design, for the sintering of iron powder structural parts, usually consists of four
zones serving different purposes:
1) the so-called burn-off zone, where the lubricants (contained in the compacts) are
burned off between 250 and 700°C ,

2) the hot zone, where the iron powder parts are sintered at 1120 - 1150°C,

3) the so-called carbon restoring zone, where superficially decarbonized parts can be
recarbonized at 800 - 900°C, and

4) The cooling zone, where the sintered parts are cooled down to approx. 250-150°C,
before being exposed to air. See schematic drawing at Fig. 6.19. Ideally, each one of
these zones would require its own specific combination of flow rate, flow direction and
composition of atmosphere. However, ideal conditions are not achievable. To find
practicable compromises and provide adequate furnace designs, is the business of the
manufacturers of industrial sintering furnaces. Within the frame of this chapter, we
cannot enlarge on problems of furnace design; instead, we refer to the competence and
specific know-how of furnace makers.

Thermodynamical problems

Arise from the circumstance that a sintering atmosphere of given composition changes
character with temperature. For instance: the character of endogas changes with rising
temperature from carbonizing to decarbonizing, and the character of hydrogen (with
traces of water vapor) changes with falling temperature from reducing to oxidizing.
Furthermore, the atmosphere changes its composition while reacting with the sintered
material. Reduction of residual oxides enriches the atmosphere with water vapor;
decarbonization of sintered material enriches the atmosphere with carbon monoxide. In
the following paragraphs, we will discuss these problems in more detail.

Advantages of Sintering:-

 Allows making complex geometries

 Saving material

 High precision

 Stability in the process of big series

 Good mechanical characteristics

 Products ready for assembly

 Cost economy compared with other processes

Disadvantages:-

 100% sintered (iron ore) cannot be charged in the blast furnace.

 Sintering cannot create uniform sizes.
 Micro- and nano-structures produced before sintering are often destroyed.
Sintering Furnaces:-

In industrial powder manufacture there are two types of furnaces, batch and continuous.
In a batch furnace low quantities of parts are placed in the furnace, undergo the entire
sintering process and are removed.

Continuous furnaces provide flow through production and have three zones for the
three stages of the manufacturing process, (preheat, sinter, and cool down). A moving
belt carries a continuous supply of parts through the chambers. Heat doors can rapidly
open and close to allow parts through, while keeping heat in. The belt travels at the
exact speed to give parts the correct amount of time in each chamber. Consistent
products and high productivity rates make continuous furnaces the most common
choice for powder sintering. While batch operated furnaces have a lower productivity
rate and are less often used, they do provide more control of the atmosphere and hence
part purity. Vacuum atmospheres can generally only be provided by batch furnaces.
7. Selective laser sintering:
For metal 3D printing, Selective Laser Melting.

7.1. Selective laser sintering (SLS):

Is an additive manufacturing (AM) technique that uses a laser as
the power source to sinter powdered material
(typically nylon/polyamide), aiming the laser automatically at points in
space defined by a 3D model, binding the material together to create a
solid structure. It is similar to Selective Laser Melting (SLM); the two
are instantiations of the same concept but differ in technical
details. Selective laser melting (SLM) uses a comparable concept, but in
SLM the material is fully melted rather than sintered, allowing different
properties (crystal structure, porosity, and so on). SLS (as well as the
other mentioned AM techniques) is a relatively new technology that so
far has mainly been used for rapid prototyping and for low-volume
production of component parts. Production roles are expanding as
the commercialization of AM technology improves.
 An SLS machine being used at the Centro Renato Archer in Brazil.

7.2. Technology:
An additive manufacturing layer technology, SLS involves the use
of a high power laser (for example, a carbon dioxide laser) to fuse small
particles of plastic, metal, ceramic, or glass powders into a mass that has
a desired three-dimensional shape. The laser selectively fuses powdered
material by scanning cross-sections generated from a 3-D digital
description of the part (for example from a CAD file or scan data) on the
surface of a powder bed. After each cross-section is scanned, the powder
bed is lowered by one layer thickness, a new layer of material is applied
on top, and the process is repeated until the part is completed.
 Selective laser sintering process
1-Laser. 2- Scanner system. 3- Powder delivery system. 4- Powder delivery piston. 5- Roller. 6-
Fabrication piston. 7- Fabrication powder bed. 8- Object being fabricated (see inset). A- Laser
scanning direction. B- Sintered powder particles (brown state). C- Laser beam. D- Laser
sintering. E- Pre-placed powder bed (green state). F- Unsintered material in previous layers.

Because finished part density depends on peak laser power, rather

than laser duration, a SLS machine typically uses a pulsed laser. The
SLS machine preheats the bulk powder material in the powder bed
somewhat below its melting point, to make it easier for the laser to raise
the temperature of the selected regions the rest of the way to the melting
point.

In contrast with some other additive manufacturing processes, such

as stereolithography (SLA) and fused deposition modeling (FDM),
which most often require special support structures to fabricate
overhanging designs, SLS does not need a separate feeder for support
material because the part being constructed is surrounded by unsintered
powder at all times, this allows for the construction of previously
impossible geometries. Also, since the machine's chamber is always
filled with powder material the fabrication of multiple parts has a far
lower impact on the overall difficulty and price of the design because
through a technique known as 'Nesting' multiple parts can be positioned
to fit within the boundaries of the machine. One design aspect which
should be observed however is that with SLS it is 'impossible' to
fabricate a hollow but fully enclosed element. This is because the
unsintered powder within the element can't be drained.

Since patents have started to expire, affordable home printers have

become possible, but the heating process is still an obstacle, with a
power consumption of up to 5 kW and temperatures having to be
controlled within 2 °C for the three stages of preheating, melting and
storing before removal.

7.3. Materials:
Commercially-available materials used in SLS come in powder form and
include, but are not limited to, polymers such
as polyamides (PA), polystyrenes (PS), thermoplastic elastomers (TPE),
and polyaryletherketones (PAEK). Polyamides are the most commonly-
used SLS materials due to their ideal sintering behavior as a semi-
crystallinethermoplastic, resulting in parts with desirable mechanical
properties. Polycarbonate (PC) is a material of high interest for SLS due
to its high toughness, thermal stability, and flame resistance; however,
such amorphous polymers processed by SLS tend to result in parts with
diminished mechanical properties, dimensional accuracy and thus are
limited to applications where these are of low importance. Metal
materials are not commonly used in SLS since the development
of selective laser melting.