MM 362

Ceramics and Glasses

Spring Semester 2020, FMCE, GIKI

Lecture 22-24

Instructor:
Muzammil Irshad
Lecturer

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 Ceramic Sintering:
Sintering:

 Sintering (Firing) of ceramic materials is the method involving

consolidation of ceramic powder particles by heating (or along with
pressure) the “green” compact part to a high temperature below the
melting point, when the material of the separate particles diffuse to the
neighbouring powder particles.

 Powder compact is usually around 50% of its final theoretical density.

Full densification is achieved by sintering at high temperatures.

 The sintering or firing process provides the energy to encourage the

individual powder particles to bond or “sinter” together to remove the
porosity present from the compaction stages.

 During the sintering process the “green compact” shrinks by around 40

vol %.  Diffusional mass transport leads to the formation
of a dense body.

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Ceramic Sintering: Kiln/furnace for sintering of ceramics

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Ceramic Sintering
What is Sintering:

 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).

 Sintering involves a process of transformation from a porous

state to a state of dense material and it must involve the process
of neck formation and growth.

 Sintering can be accomplished by using pressure (e.g., hot

pressing, hot isostatic pressing [HIP or HIPing]) or without
pressure (e.g., pressureless sintering in air).

 Liquid phase sintering (LPS) is a process for forming high

performance, multiple-phase components from powders. It
involves sintering under conditions where solid grains coexist
with a wetting liquid.
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Ceramic Sintering (Porous Ceramics)
Porous Ceramics:

 Sintering route is also adopted to produce porous ceramics for various

engineering applications, including biomedical applications.

To fabricate ceramics with a desired porosity, two strategies can be adopted:

1. Powders can be mixed with volatile material (naphthalene, poly(methyl

methacrylate) [PMMA], polyvinyl alcohol [PVA], sugar, etc.) and
subsequently can be sintered. The idea is that the evaporation of the volatile
material will leave pores.

2. Sintering at a temperature much lower than that used to obtain a dense

ceramic can also produce a porous material.

How we can control volume fraction and size of porosity ?

With the selection of the amount and size of volatile material (e.g. PVA), a porous
ceramic with the desired volume fraction and size of porosity can be obtained.

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Ceramic Sintering
Selective Laser Sintering:

 Selective laser sintering is an additive manufacturing technique

that uses a laser as the power source to sinter powdered material.

 Powder is heated just below its melting point. This causes the
powders to sinter together forming the solid 3D model which was
intended to be made.

 The process often starts by creating a CAD file..

 When the laser is directed to the platform, it begins tracing

cross-sections of the designed digital object onto the powdered
material.

 Since the product lies in a bed of powder, no supports are

necessary.

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Ceramic Sintering
Tube Furnace Sintering:

 It involves compacting a ceramic powder into a mold and

heating it for extended periods.

 The powder must not be heated to the point of melting,

instead it must be kept under sustained temperatures to
encourage powder particles to diffuse into one another,
forming crystalline bonds.

 This results in a solid material mass with exceptionally

dense, high-strength mechanical properties.

 Sintering process (i.e. sintering temperature, holding time,

heating rate, cooling rate etc) could be programmed by using
control unit.

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 Ceramic Sintering (Microwave Sintering)

 It improve the consolidation efficiency and reduce the processing

cycle-time, in order to attain substantial energy and cost savings.

 Microwave sintering provides efficient internal heating, as energy is

supplied directly and penetrates the material.

Importance especially in comparison to conventional sintering:

 Heat is generated throughout the material, thus avoiding significant
temperature gradients between the surface and the interior.

 This is particularly important for manufacturing of specialty ceramic

materials such as bioceramics and electroceramics.

Benefits comparison to conventional sintering ?

Ceramics produced with limited grain coarsening, leading to
accelerated densification, uniform and fine-grained microstructures,
with enhanced mechanical performance.
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Ceramic Sintering (Spark Plasma Sintering)
Spark Plasma Sintering (SPS) or Pulsed electric current Sintering (PECS) / Fast Assisted Sintering
Technology, (FAST):

 Spark plasma sintering (SPS) is a sintering technique utilizing uniaxial force and a pulsed (on-off) direct
electrical current (DC) under low atmospheric pressure to perform high speed consolidation (5-20minutes)
of the powder.
 Pulsed direct current used to heat the specimens.

 SPS allows much faster heating rates 600ºC/min and shorter sintering times and lower sintering
temperatures

 SPS Allows the application of very high heating and cooling rates, enhancing densification over grain
growth promoting diffusion mechanisms lower sintering temperatures, holding times and, finer grain size are
usually obtained by means of SPS.

Is SPS economically viable? It depends on the use of the final product.

(sintering without pressure is more desirable sintering method to produce ceramic products, mainly due to its simplicity
and cost when compared to other methods).

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Spark Plasma Sintering (SPS) or Pulsed electric current Sintering (PECS) / Fast Assisted Sintering
Technology, (FAST):
 SPS systems likewise comprise a water-cooled vessel, a hydraulic pressing system, and a computer-aided
process control

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Ceramic Sintering (Spark Plasma Sintering)
SPS:
P
Upper Electrode Oil Pressure
System

On-Off DC Pulse
Powder

Generator
Upper
Punch
Thermocouple Die
Controller
Pyrometer
Lower
Punch
Temperature
Pressure
Vacuum Current - Voltage
chamber Vacuum

Lower Electrode

P
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 Ceramic Sintering (Spark Plasma Sintering)

 The die serves as a heating source as well as a pressure die.

 Application of pulsed electrical field (Resistance heating )
 Pressure to achieve high heating rates and fast sintering of
powder P
 Fast cooling rates can also be achieved Pulse Current
Powder

Pulse Current
On-Off DC
Thermo
-couple
Die

Punch

Electrode

P
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Ceramic Sintering
Sintering Mechanism:

 Plasma heating- micro-spark electrical discharge in the gap between powder particles
results in localized and momentary heating of the particles surfaces up to several thousands
ºC

The purified surface layers of the particles melt and fuse to each other forming “necks”.

Joule heating- joule heat is generated by the electrical current flows from particle to
particle through the necks connecting them.

 Increases the diffusion of the atoms/molecules in the necks enhancing their growth.

 Localized character of heating allow rapid temperature rise and drop, which diminish
coarsening of grains.

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 Sintering Mechanism

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Sintering Mechanism at Atomic Scale

(5) Viscous or creep flow

 Viscous flow of particles is from areas of high stress to low stress and can lead to densification

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Ceramic Sintering
Applications of SPS process:
 SPS processes to synthesize and consolidate ultra hard & ultra high
temperature materials and composite (Boron carbide–aluminum
composites, Titanium diboride–boron carbide composites).

 The SPS technique can enhance the sinterability of Si3N4 producing

dense materials with controlled grain growth and phase transformation at
reduced temperatures compared to CS processes.

 SPS as the best option to attain fully dense CNTs containing composites
avoiding the nanotubes degradation

 SPS is shown to be a highly efficient technique for densification of YSZ

at temperatures 100–200 ºC lower than that needed by HP and also limited
grain growth
Ceramic Sintering
Effect of Sintering Parameters (Microstructure Control):
Reduction of grain size is required to improve some properties, such as
strength, toughness and wear resistance in ceramics.

1. In order to obtain ultra-fine ceramic microstructures,

nanocrystalline powders can be used.

2. A controlled grain size with high densification could be achieved by

adequate control procedures of the heating curve (grain boundary
diffusion).

3. To achieve nanometric grain sizes is through addition of solutes or

particles of a second phase in single-phase ceramics, which reduce
the grain boundary mobility or fix the grain boundary (e.g. TiO2
addition in Y2O3)

 Grain boundary inhibition can be due to the pinning effect, which is

associated with particles locations at grain boundaries. SEM micrographs of alumina samples
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Ceramic Sintering (Case Study) Al2O3-Ni Composite Prepared by SPS:
 Powder mixture pressed at a pressure of 50 MPa and heated at a rate of 100 °C/min. All of the samples were
sintered at 1400 °C with a holding time of 10 min.

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Ceramic Sintering (Case Study)
Effect of Sintering Parameters (Microstructure Control):

Density and grain size of Al2O3 compacts after sintering at various temperatures for 1 hour.
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Ceramic Sintering (Case Study)
Comparison between a conventional sintering process and by SPS
(Spark Plasma Sintering) consolidation of WC-6Co (%wt):
Sintering parameters of conventional sintering and SPS process.

 Full densification is
difficult in conventional
sintering

 The cobalt works as a binder and it decreases significantly the sintering temperature due to the liquid formation between the
particles of WC
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Ceramic Sintering (Case Study)
Comparison between a conventional sintering process and by SPS
(Spark Plasma Sintering) consolidation of WC-6Co (%wt):
Conventional Sintering SPS

21 Vickers Hardness Comparison

Relative density

Conventional sintering :
 Fully densified at 900 °C for 1 h.

Spark plasma sintering :

 99% at 700 °C. for 1h.
 High density 600–700 °C for 5min.
Ceramic Sintering (Kinetics)

kinetics of sintering are dependent on many variables, including:

particle size and packing,

 Sintering atmosphere

 Degree of agglomeration

 Temperature

 Presence of impurities.

 Eliminate the agglomerates in the green body resulted in a

powder compact that densified much more readily
 Ceramic Sintering

(a) Initial stage of sintering model represented by

spheres in tangential contact

(b) Near end of initial stage; spheres have begun

to coalesce,

(c) Intermediate stage; grains adopted shape of

dodecahedra, enclosing pore channels at grain
edges,

(d) Final stage; pores are tetrahedral inclusions at

corners where four dodecahedra meet.

In geometry, a dodecahedron is any polyhedron with twelve flat

faces.
 Ceramic Sintering

Usually the activation energies for surface, grain boundary, and

lattice diffusivity increase in that order.

Q: Surface diffusion is favoured at lower or higher temperatures?

Surface diffusion is favored at lower temperatures and lattice
diffusion at higher temperatures.

 Grain boundary and surface diffusion are preferred over lattice

diffusion for smaller particles.

 Lattice diffusion, however, is favored at long sintering times, high

sintering temperatures, and larger particles.
Ceramic Sintering

5min, 20 min, 1 hr and 120 min

Ceramic Sintering

 Grain size is a major factor determining many of the electrical, magnetic, optical, and mechanical
properties
 Ceramic Sintering

 Factors Affecting Solid State Sintering

Temperature. Since diffusion is responsible for sintering, clearly increasing temperature will greatly enhance the sintering
kinetics, because D is thermally activated.

Green density. Usually a correlation exists between the green (prior to sintering) density and the final density, since the
higher the green density, less pore volume has to be eliminated.

Uniformity of green microstructure.

Atmosphere. The effect of atmosphere can be critical to the densification of a powder compact.
 atmosphere can enhance the diffusivity of a rate-controlling species, or Gases increase pressure
Impurities

Particles Size and distribution

 Ceramic Sintering

Q: Which of the following transformations can be considered displacive and which can be considered reconstructive:
i) melting, ii) crystallization

Q: What are the roles of impurities and their effects during sintering?
 They aid in sintering: purposefully added to form a liquid phase
 Suppress coarsening by reducing the evaporation rate and lowering surface diffusion
 Suppress grain growth and lower grain boundary mobility
 Enhance diffusion rate.