Spark Plasma Sintering process

Overall Structure of the Lecture

Fundamentals

Fundamentals of Sintering as a process to consolidate powders

Spark Plasma Sintering : Process description

Spark Plasma Sintering : Simulation results

Broad objectives:

This lecture would serve the following objectives:

The fundamental concepts of Sintering Process
Process description of Spark Plasma Sintering
Spark Plasma Sintering Process Simulation results
 Sintering
Sintering refers to the process of firing and
consolidation of powders at T> 0.5Tm, where
diffusional mass transport leads to the formation
of a dense body.
Classification:

Solid state sintering

Liquid phase sintering

Basic phenomena occurring during sintering
under the driving force for sintering
Global Thermodynamic Driving Force
 Sintering is an irreversible process in which
total free energy of the system is decreased by
decreasing total surface area i.e. replacing S/V
interfaces with S/S interfacial area.
dG dA dA 0
ss ss sv sv

Sintering will stop, when dG = 0

dA
ss sv
 dA
sv ss
Densification during sintering
Densification curve of a powder compact
Sintering Mechanisms: Three particle model

Rate limiting stage in solid
state sintering is the diffusion of
slowest diffusing ions along its
fastest path

Ambipolar diffusion occurs

in case of ionic solids

Surface diffusion leads to

particle coarsening, instead of
shrinkage

Only lattice diffusion (at

final stage) and GB diffusion
(mostly in intermediate stage)
leads to densification.
Pore size/shape during sintering

before sintering
during/after sintering
Pore movement and pore shape during grain growth

Pore morphology changes during grain boundary migration for pores attached to
grain boundary. The total elimination of porosity depends on the location of pores,
pore size as well as on densification-grain size trajectory

The grains at triple junctions shrink and resultantly, pores coalesce leading to decrease
in number of pores and pore growth
 Grain growth in ceramics
Normal/Continuous Vs.
Abnormal/discontinuous/exaggerated grain growth

The grains with 6 grain edges: Equiaxed grains

without any curvature

Spark plasma sintering (SPS)

Benefits:

Reduced sintering time.

Good grain to grain bonding

Clean grain boundries

Initial activation of powders by pulsed voltage.

Resistance sintering under pressure.
Phenomenology of SPS:
- release of electrical energy through a porous powder compact
- breakdown of surface films
- Arcing at pores leading to enhanced mass transport to neck
 SPS effect

Simultaneous application of mechanical

pressure and high power pulse source
(upto 6 kA).

Pulsed direct current leading to cleaning and

surface activation of powders.

Generation of electric discharge at the neck

region
 Neck formation due to localized heating

Joules heating: localized

temperature increment

In the presence of pressure and electric current, localized necking

occurs faster due to joule heating. Consequently, the temperature
raises very fast (faster than conventional sintering and Hot
pressing) and the densification is completed within few minutes
 Experimental: Spark Plasma Sintering

Heating rate : 600 650 K/min; Maximum pressure: 50-60 MPa

DC Voltage : 5 10 V; Pulse frequency: 30-40 kHZ
Vacuum: 60-70 mtorr; Sintering time: 5 minutes
When spark discharge appears in the gap between the particles of a material, a local high temperature state occurs. This causes vaporization and the melting of the
surfaces of the powder particles during the SPS process; constricted shapes or necks are formed around the contact area between the particles. These necks
gradually develop and plastic transformation progresses during sintering, resulting in a sintered compact of over 99% density. Since only the surface temperature of
the particles rises rapidly by self-heating, particle growth of the starting powder materials is controlled.
 Pressure Pressure
Pressure
P owder Particles( A)

Spark plasma Molten layer

Electrons Vaporization layer Discharge column
Vacuum (Spark Plasma)
ionization
Ar/air
Vaporization layer
ion Molten layer
 P owder Particles( B) pressure
Pressure pressure
(I) Initial stage of spark discharging (II) Generation of spark plasma (III) Vaporization and melting
by ON-OFF pulse energization action on the particles surface
Pressure
Anode
Pressure

Spark impact pressure Thermal diffusion

Electromigration
Field diffusion layer
At neck (displacement) and plastic
deformation
Vaporized particles
Cathode
(IV) Generation of spark V) Enhanced neck
impact grow
pressure, th in
sputtering the
of prese
vaporized/ nce
molten of
particles spar
k
plas
ma
 SPS process (contd..)

The pulsed discharge achieved by the application of an on/off low

voltage (~ 30 V) and high current (> 600 A). The duration of each
pulse varies between 1 and 300 ms, between 2 and 30 ms.

The subsequent step comprises the application of a DC current at

a level dependent on the powder type. The pulsed and direct current
may be applied simultaneously or sequentially.

For SPS Process, electrical discharge per se does not

consolidate powders and, therefore, some additional effects are
needed to increase the final density (pressure application and/or
higher temperature than that created by electrical discharge

Pressure applied at constant/variable level during the process.

o
SPS sintering temperatures range from low to over 2000 C, which
o
are typically ~ 200-500 C lower than conventional sintering

Vaporization, melting and sintering completed in short periods of ~ 5-20

minutes, including temperature rise and holding times
 Physics of SPS process

Formation of small capacitors at the contact between particles/at

gap around the contact.

Electrical discharges are generated across these capacitor

gaps. The interfering surface oxide films are pierced beyond a
certain voltage level, depending on the dielectric strength of
oxide layer. This takes place when the arcing across the particles
leads to achieving the breakdown voltage and electrical
breakdown of dielectric film on the powder particle surface.

Alternatively, the electrical discharges around the contacts may

generate plasma, that is, an ionized gas between the powder
particles.

The above phenomena collectively contribute to the physical

activation of the powder particle surface. The physical activation
combined with faster densification at lower temperatures reduces
grain coarsening and retains a finer microstructure.
 SPS process

Three mechanisms may contribute to field assisted sintering:

activation of powder particles by pulsed current

resistance sintering

pressure application

This activation is unique and provides main difference from more

conventional resistance sintering processes (hot pressing).

The surface activation results in clean grain boundaries. The

grain boundary area shows direct grain-to-grain contact, which
is attributed to the physical activation of powder particle
surfaces during pulsed current application i.e. enhanced grain
boundary diffusion process.
 Effect of pulsed DC

Formation of capacitor banks at the surface insulating films.

Generation of electrical discharges across the capacitors

(might result in plasma).

Discharges manifested by the presence of arc, aiding in

material transport.

Localized heating of powder surfaces.

Breakdown of insulating films due to thermal and electrical

breakdown.

Enhanced diffusion (sintering) kinetics, clean interfaces and

good grain to grain bonding.
Phenomenology of SPS:
- release of electrical energy through a porous powder compact
- breakdown of surface films
- Arcing at pores leading to enhanced mass transport to neck
 SPS effect

Simultaneous application of mechanical

pressure and high power pulse source
(upto 6 kA).

Pulsed direct current leading to cleaning and

surface activation of powders.

Generation of electric discharge at the neck

region

Temperature gradient across powder compact strongly sensitive to both
power input and thermal conductivity.

No significant difference in gradient observed for high thermal conductivity

(40 W/m.K or above)
 Neck formation due to localized heating

Joules heating: localized

temperature increment

In the presence of pressure and electric current, localized necking occurs faster due to joule
heating. Consequently, the temperature raises very fast (faster than conventional sintering
and Hot pressing) and the densification is completed within few minutes

Because of faster heating rate, initial stage of sintering i.e. surface diffusion
avoided

Localized increase in temperature at particle/particle contact leads to faster

mass transport process; D = f (T, ECD) under electric field