Mass Transport Review and

Kinetics of Sintering

Transport Mechanisms determine how mass flows in reponse to the driving

force for sintering
There are 2 mechanism, both contribute to neck growth

Remember neck growth calculation using neck diameter X via surface transport does
not produce shrinkage i.e., it does not help density increases or densification. Here
Mass just gets repositioned on the pore surface to lower surface area and to remove
curvature.

Bulk Transport helps densification. See below the mass is moved between
two internal positions. i.e, mass that grows the sinter neck comes from
inside the body

Plastic flow is important during heating before dislocation population anneals out of the
material.
Surface energy is generally insufficient to generate new dislocations, so sintering
corresponds to declining dislocation density and declining role from plastic flow.

Viscous flow Sintering

Application in glasses and polymers

Here particle coalesce at a rate which depends on particle size and material
viscosity
Viscous flow is also seen in Metals. Here liquid phase form on the grain
boundary
The junction of 2 grains is a grain boundary (see bonding is not there or
negligible) hence provides path for rapid diffusion.
With sufficient grain boundary area, grain boundary diffusion dominates
sintering. Example: Powdery substances (metals) melt faster than a solid metal
piece.
Grain growth and gain boundary elimination is bad for sintering.
Note: Amorphous material lack grain boundaries.

This plot is a characteristic plot for viscous

flow sintering

See High
temperature
decreases
viscosity
hence neck
growth
should
progress with
high
temperature

A very linear decrease in

volume is expected with
increase holding time for a
specific material exhibiting
viscous flow.

Temperature is a Kinetic Parameter which decides

sintering rate

Surface Diffusion

The 3 Steps of Surface Diffusion

1. Atom breaks the existing bonds typically surface kink

(defective site), which is on the surface
2. The atom now tumbles (Motion) across or jumps
3. Atom finally finds a vacancy or a atomic sink thus
repositioning itself. Hence there is no shrinkage
The product of population of defective sites Pdefect and
probability of motion Pmotion between sites gives net diffusion
mobility M. Here both probabilities are thermally activated ,
hence

VOLUME DIFFUSION
Atom exchange with vacancies, hence also
known as
lattice diffusion

Bulk Transport helps densification. See below the mass is moved between
two internal positions. i.e, mass that grows the sinter neck comes from
inside the body

Plastic flow is important during heating before dislocation population anneals out of the
material.
Surface energy is generally insufficient to generate new dislocations, so sintering
corresponds to declining dislocation density and declining role from plastic flow.

Two dimensional
representation of a atom
vacancy exchange
During sintering each atom
changes position 6 times per
second
Vacancy flow to
the
inter-particle
grain boundary

Vacancy interact
with dislocations

Volume diffusion adhesion

Volume diffusion
sintering involves the
motion of vacancies
along these paths

Grain Boundary Diffusion

Application: Most metals
Grain boundaries form within
necks between individual
particles as a consequence of
random grain contacts leading to
misalignment of crystals

The pre-exponential factor (AA) is part of the

Arrhenius equation, which was formulated by the
Swedish chemist Svante Arrhenius in 1889. The
pre-exponential factor is also known as
the frequency factor, and represents the frequency of
collisions between reactant molecules. Although
often described as temperature independent, it is
actually dependent on temperature because it is
related to molecular collision, which is a function
of temperature.
Source:
http://chemwiki.ucdavis.edu/Core/Physical_Chemistry/Kinetics/Mo
deling_Reaction_Kinetics/Temperature_Dependence_of_Reaction
_Rates/The_Arrhenius_Law/The_Arrhenius_Law%3A_Preexponential_Factors

It is sensitive to
impurities
Crystal orientation
temperature
QB is activation energy and DBO is the frequency pre-exponential

Dislocation Motion- Climb and Slip

Dislocation climb is due to vacancy absorption
Dislocation glide is due to surface stresses
Densification rate ( here is defined as the change of porosity divided by
change of time t) improves since dislocation climb occurs with pore
elimination

is surface stress from pore curvature, is atomic volume, Dv is diffusivity, R

is gas constant, T is absolute temperature and is dislocation spacing.
Volume diffusion rate is increases 100 folds by dislocations in the neck
region.

Initial Stage Sintering Equations