Binder Burnout

The first step of subsequent production process is the burnout of polymeric binder by
thermal treatment (binder burn-out).
In ceramic processing, polymers are often added to ceramic particles to allow for higher
densities and sufficient green strength. The green body, or pre-fired ceramic, must have
sufficient strength to hold its shape after being pressed.
Binder burnout is a processing step performed before sintering, where the green body is
heated until the polymer binder is burned out of the ceramic.
The speed of this binder burn-out must be controlled very well. If the speed is too high,
then micro-cracks are produced in the green body, because the created gases do not have
enough time to diffuse out from the inside. Otherwise, if the speed of the binder burn-out is
too slow, then much time is consumed, leading to an increase in production effort.

Rahaman

Binder Burnout

The heating rate should be low at

temperatures where there is high
Mass loss
or
use a heating profile that leads to near
constant mass loss in the green body

constant mass loss rate

Rahaman

Sintering
Almost all ceramic bodies must be sintered to produce a microstructure with the required properties.

Sintering is the process by which ceramics are densified. Sintering is done because ceramics have
very high melting temperatures and reactive melts. In sintering, the green ceramic is heated to a high
temperature, below the melting point of the ceramic, where high rates of diffusion are possible. The
ceramic particles are joined into a solid monolith through diffusional movement of atoms.

DRIVING FORCE FOR SINTERING

Driving forces for sintering lowering of the free energy of the system
1. the curvature of the particle surfaces
2. an externally applied pressure, and
3. a chemical reaction.

RahamanBritannica.

Surface Curvature

The surface free energy associated with the system of particles

E : decrease in surface free energy of the system
V : is the molar volume
: is the specific surface energy
a : is the radius

Taking = 1 J/m2, a = 1 m, and Vm = 25 x10-6 m3/mol, then

Es = - 75 J/mol
Important note
In most text books it said that the driving force for sintering is the decrease in surface free
energy.
Surface curvature and surface area are related to each other. The smaller the particle
size the higher the surface area and therefore surface free energy for sintering.
The above explanation is the same decrease in surface free energy.

RahamanHiemenz.

Applied Pressure

Externally applied pressure normally provides the major contribution to the

driving force when the pressure is applied over a significant part of the heating
process as in hot pressing and hot isostatic pressing
The external pressure does work on the system of particles
Pa is the applied pressure and
Vm is the molar volume.
W : the driving force for densification due to the application of an external
pressure

P= 30 MPa, which is a typical value of the stress applied in hot

pressing, and Vm = 25 x10-6 m3/mol, then W = -750 J/mol.

RahamanHiemenz.

Chemical Reaction

R is the gas constant (8.3 J/mol),

T is the absolute temperature, and
Keq is the equilibrium constant for the reaction.
Taking T = 1000K and Keq = 10, then G = -20,000 J/mol.
Important Note
This decrease in energy is significantly greater than the driving force due to an
applied stress. In practice, a chemical reaction is hardly ever used deliberately to
drive the densification process in advanced ceramics because microstructure
control becomes extremely difficult when a chemical reaction occurs concurrently
with sintering

Rahaman

Mechanisms of Diffusion

Path of matter transport and diffusion along the major paths gives rise to the major
mechanisms of matter transport:
Lattice diffusion (also referred to as volume or bulk diffusion),
Grain boundary diffusion, and
Surface diffusion.

Rahaman Askeland

Lattice Diffusion

Lattice diffusion takes place by the movement of point defects through the bulk
of the lattice. Depending on the type of defects (vacancy or interstitial), lattice
diffusion can occur by the vacancy mechanism or the interstitial mechanism.
Vacancy and interstitial diffusion are by far the most important lattice diffusion
mechanisms.

Rahaman Askeland

Grain Boundary Diffusion

In polycrystalline materials, the crystals or grains are separated from one another
by regions of lattice mismatch and disorder called grain boundaries. Because of the highly defective nature
of the grain boundary, we would expect grain boundary diffusion to be more rapid than lattice diffusion in
the adjacent grains.

For example responsible for the shape of porosity

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Surface Diffusion

The free surface of a crystalline solid is not perfectly flat (Fig. 3.19). It contains
some vacancies (as in the bulk of the crystal), terraces, kinks, edges, and adatoms. The
migration of vacancies and the movement of adatoms provide the main mechanisms of
surface diffusion. The diffusion process is assumed to be confined to a thin surface layer
having a thickness of 0.51 nm.

RahamanHiemenz.

Solid stage sintering

Stages of sintering

The sintering stages represent the geometric progression involved in transforming the powder
compact into a strong, dense object.
depending on the conditions, sintering stages might begin with loose powder or nearly full
density deformed particles.
Here the assumption is that particles are undeformed and in point contact. Sintering stages from
a loose powder to isolated, nearly spherical pores.

RahamanHiemenz.

Mechanisms of Mass Transport

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