How to process ultra fine ceramics?

Suppression of particle/grain coarsening while

augmenting densification is essential.

Lowering of sintering time and temperature is the

solution.
Can pressureless sintering maintain
nanocrystalline grain size in dense ceramic
compacts????

Normally higher temperature and longer holding

time fails to restrict considerable grain growth.

Two step sintering scheme, holding at lower

temperature after reaching peak densification
temperature, allows maintaining nanocrystalline
grain size.
[ I. W. Chen et al. Nature 404 (2000) 168-171]
Nano Y2O3---- two stage sintering

Nature 404 (2000) 168.

 Nano Si3N4 ---- two stage sintering

two stage
sintering

1750C
1450C-20h
Scripta Mater. 54 (2006) 615.
Al2O3-5% Ni nanocomposite (reductionpressureless sintered @ 1773K)

Kim et al. Mat. Letters, 2003

 Processing of
ultrafine/nanoceramics
Suppression of particle/grain coarsening while
augmenting densification is essential.

Lowering of sintering time and temperature is the

solution.

Activated sintering provides the way.

Advanced Sintering techniques
Advanced Sintering techniques
 HOT PRESSING

Hot pressing causes the applied pressure to be

magnified at particle contacts and increases the rate
of densification
Hot Pressing: advanced densification route

Simultaneous application of
preessssuurre aannddhheat

Pressure

Heating rate: 5-50oC/min

Hot pressing time:

several h

Sintering atm.: Vacuum

or inert (Argon/Nitrogen)
 Densification enhancement during Hot Pressing

The external pressure contributes to additional compressive force, resulting in

enhanced mass transport in neck region
The driving force for densification is increased by one order of magnitude
 Hot Pressing: advanced densification route

High strength and purity ceramics

Hot Pressing is only suited to relatively simple shapes, with components usually
requiring diamond grinding to achieve the finished tolerances.
SiC- 30 wt% WC by hot pressing

(Ceramic International 2014)

Nanostructured Silicon Carbide
T1

Temperature
SiC Nanoceramics
~ 40 nm T2

(C)
20oC/min
40oC/min

Time (hr)

J.Am.Ceram.Soc. (2003).
Al2O3-SiC nano composite

Ceram. Int. 26 (2000) 391.

Intergranular phase in Hot pressed -Si3N4

Note the presence of intergranular glassy (amorphous) layer of

1nm thickness
High fracture strength YSZ-SiC nano composite

J. Eur. Ceram. Soc. 18 (1998) 693.

High temperature strength Si3N4-SiC nano composite

Composite A 30 (1999)425
Toughened Alumina

J. Eur. Ceram. Soc. 19 (1999) 2125.

High fracture toughness WC-Co nanocomposite

J. Alloys Compd. 312 (2000) 315.

 Machinable Ceramics

Nano BN dispersed inAlumina

Mater. Res. Bull. 37 (2002) 1401.

Machinable Ceramics

Nano BN dispersed in 3Y-ZrO2

Mater. Sci. Eng. A 397 (2005) 35.

 Nanocomposites based on Si3N4 _
increased strength due to strengthening and
reduction of amorphous grain boundary phase

Hot pressing at 16000C of

amorphous Si-C-N powders
additive ( ~ 1wt% Y2O3) at
16000C.

In-situ crystallization of
Si3N4 and SiC led to formation
on Nano/Nano composite.

Enhanced superplasticity
was observed. [M. Yoshimura et al.; Scripta Mater. 44 (2001) 1517-1521]
 Si3N4/BN nanocomposite

Si3N4 -15 vol% BN

nanocomposites (hot pressed)

Superior machinability while

maintaining strength.

[J. Am. Ceram. Soc., 85 [11] (2002) 268995]

Si3N4-based nanoccomposite

J. Am. Cer. Soc., 85 [11] 267888 (2002)

Si3N4-BN nanocomposite
Si3N4-BN nanocomposite
J. Am. Ceram. Soc., 85 [11] 268995 (2002)
 Application of pressure
Cant provide significant augmentation in
sintering kinetics because of intrinsic sintering
stress.
( = -2/r)
Sliding of grains past one another (deformation)
on pressure application leads to enhanced
kinetics.

Transformation assisted consolidation (TAC) is a

viable procedure to obtain dense nanocrystalline
ceramics.
[B. H. Kear et al. Scripta Mat. 44 (2001) 2065-2068]
 Faster sintering kinetics required

Only pressure application does not always

ensure grain growth restriction to
nanocrystalline regimes.

Faster heating rate necessary.

Gm(T) = G m+ (g /)(ToTexp(-Q /KT)dT)

0 o g

Further lowering of sintering temperature and

holding time is beneficial.

SPS promises the same

Applied pressure increases the vacancy flux from pores (vacancy sources) to GB (vacancy sinks).
However for NC ceramics, very small initial particle size and extremely small pore sizes, the intrinsic
sintering stress is higher
( = 2/r)
Sintering stress
Surface tension
Pore radius r
500 Mpa for NC as compared to that of ~5 Mpa for micrometer sized powder compact

Pressure application contributes for the increased densification kinetics via

Reduced stress due to the presence of larger interagglomerate pores
Breakage of agglomerates
Pore shrinkage via plastic deformation of grains at around homologous temperature of 0.5
(Superplastic deformation)

Appropriate selection of external stress and temperature necessary for the superplastic deformation
Longer sintering duration results in the grain coarsening.

Further lowering of sintering temperature and holding time is beneficial.

Advanced Sintering techniques
 Activated Sintering: Spark plasma
sintering (SPS)
Activated sintering refers to the process which lowers the activation
energy, allows the densification to occur at lower sintering
temperature, shorter sintering time with better properties.
Pressure assisted activation Hot pressing
Chemical activation by the addition of second phase through
chemical reaction
Physical activation i.e., applicat ion of electric current

SPS :
Simultaneous application
of pressure and heat-
similar tooHHPP

Heating by Joule effect- ----

- RReessisstaanncceeHHeeaatinngg
 Driving forces for Spark plasma sintering

Resistance heating or Joules Heating

Pressure application
Surface activation of the powder particle surface
Pressure Application
Resistance Heating Surface Activation

Dense Material

The continuous application of electric current through the sintering

period, leads to sustained activation of the powder particle surfaces
and hence triggers the sintering to occur in shorter time.
 Spark plasma sintering (SPS)
Electrical field assisted processing benefits in
sintering
feasibility to consolidate difficult-to-sinter
powders
achieving full density in shorter time
higher sintered densities at lower temperatures
significantly less processing time than
conventional sintering
finer microstructure and improved Physicho-
mechanical properties

Heating rate: upto

600K/min.

Sintering temperature
lower by 2003000C.
Initial activation of powders by pulsed
voltage.
Holding time 05 min.
Resistance sintering under pressure.
Total processing time:
20 min. Spark Plasma Sintering : a promising processing to
 Commercial SPS

instrumented pulseelectro discharge consolidation or spark

sintering under pressure (Korea)
plasma activated sintering (PAS, Japan)
pulsed electrical discharge with pressure application (Russia)
and Plasma pressure consolidation (USA).
 Sintering Mechanism in SPS

Neck formation due to localized heating

Joules heating: localized
temperature increment

Under high amount of pressure and electric current localized

necking occurs due to joule heating. In this process, the
temperature raises very fast (faster than conventional
sintering and hotpressing) and the densification is completed
within few minutes.
 SPS

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 selfheating, particle growth of the
starting powder materials is controlled.

Chapter 12 -
 Pressure Pressure Pressure
Powder Particles(A)

Spark plasma Molten layer

Vaporization layer Discharge column
Electrons
(Spark Plasma)
Vacuum
ionization
Ar/air Vaporization layer
ion Molten layer

Powder Particles(B) pressure

Pressure pressure
(I) Initial stage of spark discharging (II) Generation of spark plasma (III) Vaporization and melting action
by ON-OFF pulse energization on the particles surface
Pressure
Anode
Pressure

Thermal diffusion Electromigration

Spark impact pressure
Field diffusion layer (displacement) and plastic
At neck
deformation
Vaporized particles

Cathode
(IV) Generation of spark impact pressure, sputtering of (V) Enhanced neck growth in the presence of
vaporized/molten particles spark plasma
 SPS process
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.

The subsequent step comprises the application of a DC current at a leve

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

For SPS Process, electrical discharge by itself 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.

SPS sintering temperatures range from low to over 2000oC, which are
typically ~ 200500oC lower than conventional sintering
Vaporization, melting and sintering completed in short periods of ~ 520
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.
 go Qg

T
G (T ) G o exp(
m m
)dT
T0 kT
where Go is the starting grain size at time t = to, m is a constant, go is a
material constant, is the constant heating rate, Qg is the activation
energy for grain growth, k is the Boltzmann constant, and T is the
absolute temperature

J. Am. Ceram. Soc., 1991, 74, 12171225.

 High heating rate during SPS process
Efficient heat transfer to the powders.

Application of mechanical pressure.

Use of high power pulse source (upto 2000A).

Pulsed direct current leading to cleaning and

surface activation of powders.

Generation of electric discharge and possible

plasma!!!!
 SiC whiskers reinforced Al2O3
nanocomposites
Combination of HEBM and SPS resulted in
successful consolidation of -Al2O3 20 vol% SiCW
nanocomposite (matrix grain size ~ 118 nm).

Sintering temperature: 11250C, lower than

transformation temperature (12000C).

Mechanical properties:
Hardness: 26.2 GPa (monolithic Al2O3
hardness ~ 19 GPa)
Toughness: 6.2 MPa m1/2
[G. D. Zhan et al.; J. Am. Ceram. Soc. 87[12]
(2004) 2297-2300]
Strength obtained by various Al2O3 based
nanocomposites
1200
conventional monolithic Al2O3
1100 Al2O3 - 5 vol% SiC nanocomposite[77]
Al2O3 - 5 vol% SiC nanocomposite[100]
Al2O3 - 15 vol% SiC nanocomposite[77]
1000
Al2O3 - 18 vol% SiC nanocomposite[103]
Al2O3 - 35 vol% TiC nanocomposite[106]
Strength (MPa)

900

800

700

600

500

400

0 5 10 15 20 25 30 35 40
vol% reinforcement
Zenith of strength obtained at 5 vol% reinforcement
 Nanocomposites based on WC

WC based cermets (metallic binders) are

conventionally used for variety of applications:
Cutting tools.
Rock drill tips.
Wear parts.
Tools and dies.

With reduction in grain sizes to nano-scale, novel

applications like catalytic, microelectronic
applications are being proposed for these WC
based cermets.
 Mechanical properties of conventional
and nano-structured cermets
Toughness of conventional cermets decrease with
increasing hardness, but not so in case of nano-
structured cermets.

Hardness of conventional cermets is found to

decrease with increasing in indentation loads,
while this decrease is negligible in case of
nanostructured cermets.

Ascending rate of hardness, with decreasing

binder mean free path, in nano-structured cermets
is much higher than that in conventional ones.
 Nanomaterials based on WC

Increase in hardness by ~ 3 GPa (from 16 to 19 GPa) obtained

with SPS processed WC-Co nanocermets. [S. I. Cha et al.; Materials Science
and Engineering A351 (2003) 31]
However reduction in toughness is observed for nanocermets
compared with conventional cermets.
Indentation fracture toughness in WC/Co
composites as a function of hardness
Conventional composite samples
Nano-phase composite samples

[ K. Jia et. Al; Nanostructured Materials 10[5] (1998) 875-891]

Development of WC/ZrO2 nano-composites via Spark
Plasma Sintering (SPS) sintering
Basu et al. [Key Engg. Mat. 264-268 (2004) 2293-2296] synthesized WC
6wt% ZrO2 nanocomposites via SPS at 13000C (600K/min).

Microstructure characterised by dispersion of nano-sized

ZrO2 particles (100-150 nm), within & at the grain
boundaries of micron-sized WC grains (0.3-0.4m) -
Inter/intragranular ceramic nanocomposite.

Mechanical properties:
Superior hardness of ~ 24 GPa (Hardness of
conventional cermet: 14-16 GPa)
Moderate toughness of ~ 6-7 MPa m1/2
 Densification of WCC--6 wwt. % ZrO2 : SPS route
100

98
Relative density (%)

96

94

92

WC-6 wt. % ZrO2 (TZ-3Y)

90
1200 1250 1300
Sintering temperature, 0C
Other processing routes:
100 % density after Pressureless sintering at 1700C,1h,vacuum
Monolithic WC : > 98 % th after SPS @ 17000C

ZrO2: an alternative sinter-additive for WC

 24 8

Vickers Hardness (Hv10, GPa)

Indentation toughness, MPa

22 6

20 4
Basu et al., J. Am. Cer. Soc., 87 [2] (2004) 317-319

Hardness

m1/2
Toughness
18 2
1150 1200 1250 1300 1350
SPS temperature, oC

Pressureless sintering at 17000C, vacuum ~ 22 GPa, 4.6MPa m1/2

Monolithic WC : ~ 23-24 GPa, ~ 5-6 MPa m1/2

 Microstructural characterization: WC--66 wwt. % 3Y--ZZrrOO2

WC

WC
SPS @ 13000C
Intensity (arbitrary)

WC
t-ZrO2

25 30 35 40 45 50 55
2 (degree)
No detectable reaction between WC and ZrO2 under SPS conditions

Tetragonal zirconia retained

 WC-ZrO2 nanocomposites
SPS (13000C, 5 min) enabled
development of WC 6wt% ZrO2
Nanocomposite.
[ B. Basu et al. JACS 87[2] 9 (2004) 317]
Inter-intragranular ceramic
nano- composite with submicron
(0.3-0.4 m) WC grains and nano
(30-90 nm) ZrO2 reinforcements. 100 n m

Extremely high hardness ~ 24

GPa and wear resistance (wear rate
~ 10-8 mm3/Nm)

However poor toughness ~ 6

MPa m1/2.which increase to ~ 10
MPa m1/2 with 10 wt% ZrO2 20
20 nnm
m
 Densification of Y--TZP: SPS route
100

Relative density (%)

98

96

94

92 TZ-3Y (Tosoh grade)

90
1100 1150 1200 1250 1300

Sintering temperature, 0C
Other processing routes:

- 100 % density after Pressureless sintering @ 1450C, 2h, air

- 100% theoretical density after Hot Pressing @ 1450C, 1h, vacuum

 Mechanical Properties: SPS--pprroocceesssseedd TZP
15.0 5.0
Vickers Hardness (Hv10, GPa)

4.5

Indentation toughness, MPa

4.0
14.5
3.5

3.0

m1/2
Hardness
Toughness
14.0 2.5
1250 1200 1300
SPS Temperature, oC
Hot Pressing at 14500C, 1h, vacuum: 13.3 GPa, 4.8 MPa m1/2

Pressureless sintering at 14500C, 2h, air: 11.7 GPa, 4.9 MPa m1/2
 Microstructure: SPS - pprroocceesssseeddTZP

SPS at 13000C

t-ZrO2
Intensity (a.u)

25 26 27 28 29 30 31 32 33 34 35
2 (degrees)
Wear resistance of 3Y-TZP nanoceramics
Average grain sizes
80 nm 150 nm 200 nm 300 nm

Wear rate (X 10-6), mm3/Nm

8

3Y-TZP nanoceramics SPS 6

processed at 12000C for 5
min.
4

High hardness of ~ 14.5 2

GPa (compared to 11 GPa of
conventional ZrO2 ceramics).
0
SPS-1200 SPS-1250 SPS-1300 CS-1450
Sintering conditions
Good wear resistance.

[J. Am. Ceram. Soc 87[9] (2004) 1771]

Nanocomposites based on zirconia
Zirconia engineering ceramics are characterized
by high strength (700-1200 MPa) and fracture
toughness (2-20 MPa m1/2).

Inspite of superior toughness, conventional

monolithic zirconias application limited due to
poor hardness (10-12 GPa).

Two approaches remove this drawback:

Maintaining the ZrO2 grains in the nano-
scale range
Incorporation of harder second phases
(composite approach)

Precisely, nanocomposites based on zirconia can

enhance their applicability.
 ZrO2 toughened Al2O3 nanocomposite
Combination of HEBM and SPS at 11000C
(5000C/min) resulted in development of Al2O3-20
vol% ZrO2 nanocomposites.

Microstructure consisted of ~96 nm sized matrix

alumina reinforced with ~265 nm ZrO2 particles.

Mechanical properties:
Hardness: 15.2 GPa
Toughness: 8.9 MPa m1/2 (Toughness of
monolithic Al2O3 ~ 3-4MPa m1/2)
[Scripta Materialia 47 (2002) 737-741]
 Nanocomposites based on ZrO2/ZrB2

ZrO230vol%ZrB2 nanocomposite
processed via SPS at 12000C
(600 K/min)

Microstructure: nano-ZrO2 matrix

(100-300 nm) reinforced with
micron sized ZrB2 (2-3 m)
Nano/micro composite

Mechanical properties:
Hardness: ~ 14 GPa
Toughness: ~ 10 MPa m1/2

[J. Am. Ceram. Soc (2006)] Chapter 12 -

 Development of ZrO2-ZZrrBB2composites
15.0
9.5
14.8

14.6 9.0

14.4 8.5

KIc (MPa m1/2)

Hv10 (GPa)

14.2 8.0
14.0
7.5
13.8
7.0
13.6
6.5
13.4
13.2 6.0
Hardness Toughness
13.0 5.5
2.0 2.2 2.4 2.6 2.8 3.0
Chapter 12 -
Overall Yttria Content (mol%)