Pressureless powder shaping methods:

In die compaction processes, using mechanical and hydraulic presses, the powder

mass is shaped into green shape by applying pressure within a die where as in

pressure-less powder shaping methods, shaping of powders is done without

application of pressure. These methods include, slip casting, tape casting and gel

casting.

Slip casting/Slurry moulding:

Slip casting is a very old method and was used by potters since ancient times. A

slip is slurry of very fine metal or ceramic material suspended in water. If such a

slip is poured into a porous plaster mould, the mould will draw water from the

slurry and will build up a deposit of particles on the mould wall. In this manner an

article can be formed with an outer configuration that reproduces the inner

configuration of the plaster mould. Wall buildup during slip casting continues as

long as any slip remains in the mould. However, the rate of buildup drops off with

time, because water cannot be removed from the slip by passing through the

thickening cast wall. If a hollow cast is required, the excess slip is poured or

drained out of the mould after the required wall thickness has been achieved. This

is sometimes called drain casting.

Sometimes, instead of water, another liquid can be used for slip casting. For

example, MgO and CaO react water. Hence, a suspension of absolute alcohol or

another inert liquid is prepared and cast. Slurry moulding is similar to slip casting,

expect that the mould is solid and the powder becomes rigid due to polymer

freezing.

The casting behaviour of the slip depends on the specific gravity and viscosity of

the slip, and more importantly, on how the viscosity changes with time. The

specific gravity of the slip should be kept as high as possible, but consistent with

the appropriate viscosity parameters. The flow behaviour of slips is generally

controlled by means of small amounts of dispersion additives or deflocculants. In

clay based ceramics, the common deflocculants used are sodium silicate, sodium

carbonate, sodium phosphate and a number of organic substances such as

polyacrylates. For non-clay-based slips, strong acids or bases often give

dispersions, but certain organic substances are also suitable for this purpose. In

case the particle size distribution of a slip is wide, the slip will be difficult to

disperse and will settle rapidly, giving uneven casts and if the particle size is too

fine, the slip will cast very slowly.

The mould may consist of more than two parts, depending on the complexity of the

part. The mould parts must be tightly held together during casting, as a hydrostatic
pressure builds up in the mould due to the weight of the slip. The mould is

subsequently disassembled after casting to remove the cast.

Fig: Schematics of (a) solid slip casting (b) drain slip casting

Casting is always followed by drying and sintering. Slip casting are most effective

for longer shapes, since the equipment and tooling costs are not high. It is used to

produce monolithic shapes of turbochargers and rotors 0f Si3N4 , for production of

tubes, boats, crucibles, cones and rocket guide fins made from Mo, W , Ta and Cr

powders.
Advantages:

(1) Production of complex shapes from many ceramic materials

(2) Thin walled hollow complex shapes with uniform wall thicknesses

Disadvantages:

(1) Low production rates

(2) Relatively short mold life

(3) Time consuming finishing operations.

Tape casting (doctor blading/knife coating):

Tape casting is also known as doctor blade forming, in which the product is in

sheet or tape form from ceramic slurry. Parts of intricate shapes can be machine

stamped from pre-dried sheets of plasticized powdery materials. The process is

referred to as continuous tape casting when the blade is stationary and the

supporting surface moves, and as batch doctor blade casting when the blade moves

across the stationary supporting surface covered with slurry. The cast film is dried

to an elastic, leathery state and slit for proper handing width. The first step in the

tape casting process is the preparation of the casting slurry. The mixing and

dispersion of the slurry (maximum powder particle 5µ) are done in two stages, to

maximize dispersion but minimize degradation of the binder. After milling, the
slurry is heated, filtered and de-aired to remove agglomerates and bubbles. The

slurry is cast on a clean, smooth, impervious and insoluble surface such as

cellulose acetate. The thickness of the tape is a function of the height of the blade,

viscosity of the slurry, speed of carrier film and drying shrinkage. The casting

speed is dependent on the thickness of the tape, evaporation rate and length of the

machine, all of which control the drying time. The drying shrinkage occurs through

the thickness, and the dried thickness is about one half the blade height. Dried tape

may be used directly or stored on a take up reel.

Fig: Schematic of continuous tape casting unit

Tape defects include cracks, camber, local regions of low density, and surface

defects consisting of unacceptable roughness and large surface pores.

Tape cast products are used as capacitors, piezoelectric devices ferrite memory

substrates for catalysts, battery electrodes, brazing layers, microelectronic

substrates, coatings and thin foils.

Gel Casting:

Gel Casting improves in strength, defects like air bubbles or agglomerates are

eliminated and ceramic products have excellent mechanical behaviour, and this

process improves microstructure and homogeneity ate improved.

In Gel Casting, concentrated ceramic slurry is created by mixing a ceramic powder

and monomer solution. After the ceramic suspension is poured in to a mold to get

the desired shape and during heating the monomers will polymerizes in –situ to

form a green body with network structure. To obtain pure ceramic part, solvent

from ceramic suspension should be removed by drying in air followed by burn out

to binder removel.Finally sintering ids done to get full density.

Advantages:

(1) The same conventional ceramic forming equipment can be used in Gel Casting.

(2) It eliminates dimensional constraints in making complex parts.

(3) High green strength and good green machinibility can be achieved.

Steps involved in Gel Casting are:

Ceramic powder Dispersant Milling (organic monomers i.e. binders and initiator

addition during milling)Mixing, sieving and de-

airCastingGelationremoval from MouldDrying(to binder burn

out)MachiningSintering.

Applications:

Gel Casting is used for making of turbine rotors, ceramic rings with Al2O3, Si3N4

& ZrO2ceramic powders, metal powder forming of tool steels and Ni-base super

alloys.

Metal (Ceramic) Injection Moulding (MIM):

The machines used for the MIM process are the same as those in use in the

plastics industry with small modifications to reduce wear (hardened screw and

barrel) and to assure homogeneity (modification of screw design) during the

plastification. Therefore, standard plastic injection moulding machines undergo

modifications to optimize them for MIM with injection cylinders being adapted for

the abrasive properties of the materials used.

In Injection Moulding, the feedstock pellets are heated to a sufficiently high

temperature, they melt, and the melt is forced into a cavity where it cools and
assumes a compact shape. The purpose is to obtain the desired shape, free of voids

or other defects and with a homogeneous distribution of powder.

There are three types of Moulding Machines: reciprocating screw, hydraulic

plunger and pneumatic. The most commonly used is horizontal reciprocating screw

inside a heated barrel, which has adequate control. After the mould is filled, heat is

extracted from the feedstock through the die. Finally, the cavity is opened to eject

the hardened compact. The pressure of high content of solids raises the viscosity,

requiring high pressures during moulding. High packing pressure can result in the

compact sticking to the die wall with severe ejection problems. In brief, moulding

parameters are highly dependent on particle characteristics, binder formulation,

feedstock viscosity, tool design and machine operating conditions. The probability

of defects and the presence of distortion in sintering are highly dependent on the

moulding step.
An injection machine, reciprocating screw type

MIM process permits the production of stronger; more uniform and more complex

P/M parts. This process is more expensive than conventional PM techniques.

The process steps involved in injection moulding are:

 Selection and production of fine metal/ceramic powders

 Mixing and pelletize after addition of binders and additives to above fine

metal powders

 Moulding

 Thermal debinding/Solvent debinding

 Sintering

 Secondary operations(if required)

Powder extrusion:

Cold powder extrusion is used for metals with relatively low melting point, e.g.,

lead. The product obtained through the process has a high aspect ratio. In cemented

carbide drill making and various ceramic products, extrusion is very much applied.

There are two types of extruders: piston type and auger type. In the former, the

feed material is compressed and forced to flow down through the barrel by the

moving piston. For the displacement of material in auger feeding, the material
must not slip on the wall for the barrel and the yield strength of the body must be

less than the adhesive strength of the body on the surface. Axial rib may increase

the circumferential friction. A helix angle of approximately 20 0-250C is commonly

used. The required ratio of the auger diameter to the product diameter increases as

the yield strength of the material increases. Geometrical parameters of the die are

the entrance angle α and the reduction ratio Ro/Rf. Complex dies may contain

small channels for injecting a die wall lubricant.

During extrusion, flow occurs by the mechanisms of slippage at the wall and

differential laminar flow in the extrudate. It is evident that the pressure is highest in

the barrel and decreases along the axis of the extruder.

Some of the common extrusion defects are:

 Insufficient strength and stiffness

 Cracks and laminates

 Surface craters and blisters

 Non-uniform flow through the die

 Gradients in extrudate stiffness

(a) Piston extruder (b) Auger extruder

Hot pressing:

Hot pressing is a suitable method for densifying materials with poor sintering

behaviour. This technique, which combines powder pressing and sintering into one

single operation, offers many advantages over conventional powder consolidation.

By simultaneous application of temperature and pressure, it is feasible to achieve

near theoretical density in a wide range of hard-to-work materials. As the

resistance of metal particles to plastic deformation decreases rapidly with increase

in temperature, much lower pressures are required for consolidation by hot

pressing. Further, densification by hot pressing is relatively less sensitive to

powder characteristics – shape, size, and size distribution which are important in

cold pressing and sintering. Hot pressing parameters – pressure, temperature, time

and the working atmosphere – largely control the properties of compacts. High-

speed tool steels, superalloys, beryllium and the refractory metals are particularly

amenable to hot pressing. Hot pressing is perhaps the only method of producing

dense and fine-grained shapes of materials such as pure carbides, nitrides and

borides which are otherwise difficult to sinter due to the lack of adequate atomic

mobility at the sintering temperature.

Process and equipment:

The various steps involved in the hot pressing procedure are as follows:

1) Powder or a cold compacted preform is placed in the die mould.

2) The mould is heated either by resistance or by induction method to a

predetermined temperature.

3) The powder in the die cavity is then pressurized.

4) The temperature is steadily increased during compacting until a maximum

required temperature is reached.

5) Compacting pressure and temperature are maintained for a dwell time.

6) The mould is cooled slowly under pressure to a temperature at which oxidation

of the material will not occur.

There are many variations on the general procedure given above. In many cases, it

is preferable to apply a nominal pressure, or even the maximum required

compacting pressure, before the initiation of the consolidation cycle. This is

particularly true in the case of reactive hot pressing.

Many oxide and carbide ceramics can be hot pressed using graphite dies in the

open atmosphere. However, the die life is limited due to severe oxidation at

temperatures above 5000C. Hot compacting of refractory and reactive metal

powders demands an inert atmosphere or vacuum. Using vacuum in place of inert

gas for hot pressing offers additional advantages of removing air from the powder

body (thus eliminating the possibility of air entrapment) and also degassing it

during the initial heating up of the pressing cycle. This would enhance the activity

of the powder and thus help in sintering.

 Fig: A Hot Pressing unit

Graphite is the most common die material; carbides, titanium boride; W and Mo

are also used as a die material on a limited scale.

Different kinds if die washes,coatings,spacers,liners and sleeves are used to

overcome or decrease the die compact interaction and thus decrease contamination

and facilitates ejection of the final compact.

Induction heating is most commonly employed for heating the graphite die tooling.

Heating by radiation from resistance heating elements facilitates closer control of

temperature. However, the maximum temperature attainable by indirect resistance

heating is limited to about 18000C.

Earlier hot pressing was primarily employed to improve the densification of some

metal and metal-bonded carbide cutting tools. Currently, hot pressing as a

fabrication process is being used increasingly in the ceramic industry for the

preparation of materials with improved properties through the control of

composition, microstructure and density. Hot pressing has also been employed in

the fabrication of various high-temperature components, multiphase ceramics,

ceramic-metal systems and pressure bonding. Tungsten, tungsten-based alloys,

dispersion-strengthened aluminum and copper-based alloys, superalloys and

beryllium metal have also been consolidated by vacuum hot pressing.

Hot Isostatic Pressing (HIP):

The aim of this process is to compact materials that would normally compact only

under considerably higher pressures, or to combine the pressing and sintering

operations in one step. The pressure medium used is an inert gas. Heat is applied

by an internal furnace in the pressure vessel. In most cases the powder or work

piece is encapsulated in a gas-tight material, which can withstand high pressure

and temperature and does not react with the powder. Typical temperatures are

1000-17500C and typical pressures are 100-320 MPa or 1000-3200 bar.

Equipment and process variables:

A HIP system usually consists of five major components: pressure vessel, internal

furnace, gas handling, electrical and auxiliary systems.

Pressure vessel: The pressure vessel in a HIP system contains the high-

temperature furnace and retains the high-pressure gas. Most HIP vessels have

threaded closures. The sealing of the gas in the vessel is done with elastomeric O-

rings since the vessel temperature is kept below 2500C.

Furnace: There are different types of furnaces: radiation, natural convection and

forced convection. The common heating elements are graphite, molybdenum and

nickel/chrome.
 Hot Isostatic Pressing equipment

Hot Isostatic Pressing PM parts has the 100% dense high-performance alloy parts

on a consistent basis. Application of PM is possible where residual porosity cannot

be tolerated because of its adverse effect on key properties. HIP is used for

preparing porous parts: e.g. filters, grinding wheels and porous electrodes. Hot

isostatic pressed porous materials have larger neck growth between particles so

have better mechanical properties.

Sinter-HIP or overpressure sintering:

The widespread application of HIP is restricted by two factors:

1) Lack of HIP equipment capable of necessary high temperature.

2) Difficulty in containerizing the green powder compact.

By introducing containerless HIP a higher throughput of as much as 50%-90% can

be achieved when compared to containerized parts. The major benefit in Sinter-

HIP is the combination of sintering with the introduction of gas at the end of the

sinter cycle for HIP. This eliminates one major piece of equipment, reduces

materials handling, provides greater control of the process and saves energy and

labour costs. This process is particularly useful for cemented carbides, superalloys

and ceramic products where HIP is used. Sinter-HIP eliminates the need for

reheating the product to solidus temperature a second time, which risks abnormal

grain growth. Sinter-HIP pressure is rather low, being in the range 6-10 MPa in

comparison to that for classical HIP, since the material structures are soft in the

sintered condition.
Process variants of Hot Isostatic Pressing
Spark Sintering:

Spark sintering combines electrical energy and mechanical pressure to convert

metal powder into a solid part of desired configuration and density. It is performed

in air, vacuum or inert atmosphere using graphite or other specially developed

materials for tooling. Powder is fed into the cavity of a punch and dies assembly.

The powders used are usually electrically conductive; however non-conductive

mixtures can also be used. High density electrical energy of moderately high

frequency AC and DC combined is passed through the powder while compacting it

at relatively low pressures. Using both AC and DC energy simultaneously

accelerates and augments particle to particle bonding, which promotes more

uniform part density. At the end of the densification cycle, power is turned off and

pressure is maintained for some time while the part cools. The die stays relatively

cold during this type of hot pressing. The time taken for the entire operation ranges

from seconds to minutes depending on the material, part size, configuration,

tooling and equipment capacity. This method was originally introduced for the

production of beryllium components. It requires considerably less material and less

subsequent machining than machining from hot-pressed blocks.

In spark sintering, pressing the current helps removal of contaminants. Very high

frequencies and high current densities induce rapid densification. Pressure up to 50

MPa is applied. The process time is short and thus the method can be categorized
as rapid hot pressing method. For functionally gradient products this method of

consolidations is very useful, as different powders can be placed in different

locations and sintered as a single operation. In case of laminate metal-Intermetallic

composites too this method can be applied. Pulse plasma method is very

convenient for consolidating nanocrystalline powders. The electric current results

in local Joule heating as well as heating from the creation of localized plasma

between nearby powder particles. Since the amount of Joule heating and plasma

heating are highest in less dense areas of the compact, regions that would not sinter

well under only radiative heat and pressure experience enhanced sintering rates.

Schematic equipment for Pulse Plasma Sintering

SINTERING:

Sintering is the thermal process for consolidating powder particles in to a coherent

structure via mass transport on atomic scale. The bonding leads to improved

properties, like tensile strength, electrical and magnetic properties.

Classification of sintering techniques:

(A) Pressureless sintering

Solid-state sintering

-Single phase

-Mixed phase

-Activated sintering (e.g. W-Ni)

-Homogenization sintering (e.g. Cu-Ni)

Liquid Phase Sintering (LPS)

-Persistent LPS (W heavy alloys, cemented carbides)

-Supersolidus sintering (stainless steel, super alloys)

-Transient LPS (bronze, dental alloys)

(B) Pressure-assisted sintering

 - Hot Pressing (HP)

- Hot Isostatic Pressing (HIP)

- Sinter-HIP

Stages in sintering:

The three stages of sintering are: initial, intermediate and final stages, in the initial

stage, there is a neck formation between two toughing spheres, which in the final

stage culminates in to small closed pores.

In polycrystalline materials, atomic (ionic) transport takes place along the definite

paths from the regions of higher chemical potential to the regions of lower

chemical potential. Some of the major mechanisms of sintering a polycrystalline

material are:

 Evaporation and condensation, which operates for materials with high vapor

pressure at elevated temperatures e.g. Cr

 Diffusion: Surface , grain boundary and lattice

 Plastic flow: the green powder compacts are under stress, since the powders

are subjected to plastic deformation during compaction. Dislocations play

vital role by (i) dislocation climb due to vacancy absorption and (ii)
 dislocation glide due to surface stresses exceeding the plastic flow stress at

the sintering temperature.

 Viscous flow

For the sintering of a polycrystalline sphere on a plate of similar material, as

proceeds the neck will grow between a sphere and a plane and there will be

large negative curvature of the neck occurs. The curvature is a reciprocal of

the neck radius, ρ, with a comparatively small positive curvature of the

sphere.

Fig: Schematic two-sphere model showing

(a) non-densifying mechanism and, (b) densifying mechanism.

The above given Fig represents a two-sphere model, where two equal-sized

spheres are in contact. Fig: a, shows the non-densifying mechanism, such that there
is no change in the center-to-center distance. On the other hand, Fig: b, represents

the scheme, when the spheres penetrate each other, in addition to neck growth.

This is the densifying mechanism.

Fig: Six distinct mechanisms for sintering

The green powder compacts are under stress, since the powders are subjected to

plastic deformation during compaction. The dislocations involved would play the

vital role, particularly during early stages of sintering. Two events are possible:

1) Dislocation climb due to vacancy absorption.

2) Dislocation glide due to surface stresses exceeding the flow stress at the

sintering temperature.

Liquid Phase Sintering:

During solid-state sintering of polycrystalline powders, an important factor that

determines the densification rate is the grain boundary diffusion coefficient

multiplied by the grain boundary thickness. In case the grain boundary is replaced

by a film of liquid, many times thicker than the grain boundary, the densification

rate greatly increases because the diffusion rate in a liquid is higher than in a solid.

It is this feature which is achieved in Liquid Phase Sintering. However, only the

presence of a liquid phase is not sufficient; the melt must also wet the solid

surface. The wetting would cause spreading over the solid grains.

Stages of liquid phase sintering:

The three stages of liquid phase sintering are:

1) Rearrangement or liquid flow

2) Accommodation or dissolution-reprecipitation

3) Coalescence or solid phase bonding.

 Fig: Schematics of the three stages of Liquid Phase Sintering

Supersolidus sintering:

It involves densification by melt formation in a pre-alloyed powder compact on

heating it above the solidus temperature. In this type of sintering, solid and liquid

phases have much closer compositions. A limited amount of densification occurs

through solid-state diffusion, when the fine particles melt preferentially to form a

small quantity of the viscous liquid phase. Melting also occurs over the surfaces of

large particles and at the grain boundaries within particles. Densification occurs

through rearrangement by particle deformation.

The supersolidus sintering of high-speed PM steels:

Initially, the powder particles are sintered in the solid phase to form a skeleton

before the formation of the liquid phase. When a liquid phase appears, it
disintegrates the skeleton into almost individual solid grains. The grains rearrange

their configuration and rapid densification follows, the solid grains grow by a

solution-reprecipitation process in which material transport occurs through the

liquid phase.

Fig: Mechanism of supersolidus liquid phase sintering of high-speed steels

Supersolidus sintering of nikel-based superalloys:

When atomized loose-packed powders of alloy (15.2Cr-16.63Co-5.19Mo-3.5Ti-

4.07Al-bal.Ni) were argon sintered above 13500C, finer the particle size, better the
densification. The mean final grain size was identical to the prior particle size, but

the final grain size distribution was narrower than the prior particle size

distribution. This is due to the prior particles dissolve during the second stage of

liquid phase sintering, i.e., solution-reprecipitation.

Activated Sintering:

Activated sintering is the process by which sintering kinetics is increased and

sintering temperature is reduced, thus, giving rise to improved properties. The

amount of activator used is very small, as low as 1%.This sintering is used to

consolidate refractory metals with very high melting points, having low

diffusivities, like transition metals. By the addition of anther transition metal, like

nickel which lowers the sintering temperature of refractory metal tungsten from

20000C to 13000C by nickel diffusion on to tungsten particles and enhances the

grain boundary self-diffusion factor of refractory metals up to 5000 at 13000C.

The criteria for activated sintering based on the phase diagram of the activator (A)

and the base metal (B) are:

1) High solubility of the base metal B in the activator A

2) Activator A must have lower melting point, thus, giving a large melting point

difference of the base metal B in the activator A

3) Low solubility of the activator A in base metal B

4) High diffusivity

5) Segregation of activator at the grain boundary of the base metal.

Pressure assisted sintering:

Polycrystalline materials like ceramics and dispersion-strengthened metals and

alloys are difficult to densify by conventional solid state (pressureless) sintering,

due to the presence of strong covalent bonds, and due to the presence of hard

refractory inert dispersoids in the matrix. In conventional sintering, with prolonged

sintering the pores become stabilized and are difficult to remove from a compact

via diffusion, if the pores are filled with a gas. The inability to attain full density

can be offset by the application of external pressure on a polycrystalline powder

compact. In pressure-assisted sintering, the enhancement of densification depends

on the applied pressure, compact density, temperature and particle size. In most

pressure-assisted sintering, the applied pressure is nearly constant; thus, the

effective pressure at the particle contacts falls continuously with densification. It is

the effective pressure which determines the mechanism of densification.

Stages of pressure-assisted sintering:

Three stages-Initial, intermediate and final. Since the powder in a real system has

a particle size distribution, a preliminary stage of particle rearrangement is

expected when the external pressure is applied. In the below fig, the three stages of

solid-state sintering for alumina powder were given. In hot pressing, the curve

shifts to the left-hand side, indicating enhanced densification. During the later

stage of pressure-assisted sintering, when the relative density is greater than 90%,

the compact can be a homogeneous solid containing isolated spherical pore. The

effective stress responsible for densification is then identical with the applied

external pressure.
 Fig: Schematics of initial and final stages of pressure-assisted sintering involving

various mechanisms

Figure given above schematically shows the mechanisms – plastic yielding, power

law creep and lattice/grain boundary diffusion – for spherical powders of the same

size during pressure-assisted sintering. The left-hand side scheme is for the initial

stage, the right-hand side scheme pertains to the intermediate/final stage.