MME 467

Ceramics for Advanced Applications

Lecture 23
Examples of Toughened
Ceramics 1
Ref: Richerson, Modern Ceramic Engineering, Ch17, Marcel Dekker, 1992
Topics to discuss....

1. Self-reinforced ceramics
 Self-reinforced Si3N4
 Self-reinforced ZrC
 Transformation toughened ceramics
 Introduction

Self-reinforced ceramics
 Microstructure having enhanced toughness is produced during sintering
or heat treatment without adding a second phase.
 Examples: Si3N4, ZrC, PSZs, TZPz, and ZTCs.

Particle-reinforced ceramics
 Addition of a dispersion of second phase particles produces toughening.
 Examples: Alumina ceramics reinforced with SiC, TiB2, and TiC particle.

Whiskers and fibres reinforced ceramics

 Examples: SiC whiskers reinforced alumina, SiC or Si3N4 whiskers
reinforced silicon nitride, SiC reinforced molybdenum disilicide, glass or
carbon fibre reinforced cement, and graphite fibre reinforced glass.
 Self-reinforced ceramics

 enhanced toughness during sintering or heat treatment is

obtained by modifying a microstructure without adding a
second phase
① silicon nitride and sialon compositions – through sintering
② zirconium diboride-zirconium-zirconium carbide material
– reaction mechanism
③ zirconia materials – chemical additions
④ Transformation-toughened ceramics – phase transformation
Self-reinforced Si3N4

 Possesses two crystalline forms, a- and b- Si3N4 , distinguished

by the stacking sequence of Si-N layers in the structure.
 The b- Si3N4 phase is stable above 1420 C.

 Silicon nitride is produced either by reaction bonding or

hot pressing and sintering methods.
 Sintered silicon nitride (SSN) was found to show unusual high
fracture toughness values in ranges from 4.0–5.5 MPa.m1/2.
 Resulted from a microstructure consisting of elongated grains
of b-Si3N4 phase.
 During SSN production , 2-3 % metal
oxides additives such as MgO, Al2O3,
Ln2O3, or Y2O3 are added to a-Si3N4
particles, which are coated with SiO2.
 This forms a low-melting oxynitride
glass, which aids liquid phase sintering
and solidifies to a grain boundary glass.
 Sintering is done at 1550-1800 °C, so
the starting a-Si3N4 powder transforms
to b-Si3N4 by dissolution precipitation.
 At the sintering temperature, b-phase
precipitates out of the melt as a-phase
dissolves.
a-b transformation of SSN.
 The final microstructure has elongated
b-grains in glassy matrix.
 By exploiting the a-b transformation, elongated grains of
Si3N4 can be grown by heat treating after sintering.
 By the mechanisms of crack deflection and crack
bridging, elongated grains increase toughness.

 Material chemistry and temperature and time of sintering

affect microstructure and hence toughness of ceramic.
 Highest toughness is achieved for large grain size and for
compositions containing substantial grain boundary phase.
 The mechanical properties have been affected due to this
grain boundary phase.
 Typical Sintered silicon Reaction-bonded silicon
properties nitride (SSN) nitride (RBSN)
Density, g/cm3 3.2 – 3.9 2.2 – 3.2
Hardness, GPa 14 – 18 4–7
Toughness, MPa m1/2 3.4 -8.2 1.5 – 3.6
Modulus, GPa 280 – 320 100 – 220
Strength, MPa 400 – 1000 190 – 400

 Mechanical properties are generally

good up to 1000 °C and degradation
increases if the amount of grain
boundary glassy phase is increased,
Fig. 9.3.
 Properties of RBSN are retained to
higher temperatures since there is
no grain boundary glass phase is
present in the microstructure.

High temperature strength of silicon nitride.

Self-reinforced ZrC
 Self-reinforced ZrC ceramic material is developed by a
reactive densification process.
 B4C powder is compacted with a binder using conventional
pressing and sintering technique. The B4C preform is placed
with a controlled amount of Zr metal in a graphite mould and
heated to 1850 to 2000 °C in an inert atmosphere.
 Zr becomes molten, infiltrates the preform and reacts with
B4C to form equiaxed grains of ZrC and platelets of ZrB2.
 High toughness of platelet-reinforced ZrC/Zr matrix
composites is resulted by three mechanisms:
① crack deflection by the ZrC equiaxed particles
② crack bridging by ZrB2 platelets, and
③ crack clamping plus energy dissipation by ductile zirconium phase.
 The quantity of residual Zr can be varied either to be
completely consumed by the reaction or to be retained as
a residual metal phase.
 Strength and toughness and other properties vary with the
amount of residual Zr phase.

Vol.% Zr 4-pt. Flexure Strength, MPa Weibull Modulus

2.50 870 28
24.2 888 68

Vol.% Zr Fracture Toughness, MPa√m

1.0 11
30.0 20
Transformation toughened ceramics

 Zirconia exists in three different

crystal structures based on the
fluorite structure, Fig. 9.4.
 The liquid phase transforms into
cubic structure at about 2680 °C,
which transforms diffusionally
into the tetragonal phase at
about 2370 °C.
 Finally, the tetragonal zirconia
undergoes martensitic
transformation at about 1200 °C
and forms monoclinic crystals.
Allotropic transformation of zirconia.
 A number of dopants can be used to stabilise the cubic
phase to lower temperatures, the most important being
CaO, MgO, Y2O3 and CeO2.

(a) (b)
Binary phase diagrams of (a) ZrO2-CaO system, (b) ZrO2-MgO system.
 Retention of tetragonal ZrO2 phase metastably at RT and its
stress induced transformation to monoclinic zirconia phase is
the key of obtaining transformation toughening.

 Two classes of toughened zirconia-containing ceramics:

1. Transformation toughened zirconia
(a) Partially stabilised zirconia (PSZ)
cubic zirconia phase is partially stabilised at RT and the
remaining cubic phase is transformed into tetragonal phase
(b) Tetragonal zirconia polycrystals (TZPs)
all zirconia phases remain as tetragonal form in the structure
2. Zirconia-toughened ceramics (ZTCs)
tetragonal zirconia added to other ceramic materials to obtain
transformation toughening
Partially Stabilised Zirconia (PSZ)

 A fully stabilised zirconia crystal does not show

transformation toughening.
 The cubic phase is less than totally stabilised to form partially
stabilised zirconia (PSZ) ceramics.
 The cubic phase is then heat treated to form coherent
tetragonal precipitates.
 The heat treatment is such as to keep the precipitates small
enough so that they do not spontaneously transform within
the cubic zirconia matrix but only as a result of stress.
Typical procedure for transformation toughening in Ca-PSZ

l Composition such as 10 mol.% CaO – 90

mol.% ZrO2 is sintered at a temperature of
about 1800 °C where the cubic solid solution
(Css) field is stable.
l The material is quenched to the (Tss + Css)
region at about 1300 °C to form a
supersaturated solution, where tetragonal
l solid solution (Tss) precipitates are formed
from Css crystals.
l The material is heat treated or aged at that
temperature for about 4-5 hours until the
precipitates of Tss grow by conventional
diffusional process as coherent spheroids and
have reached the optimum size .
l Below a well defined critical size for tetragonal
l to monoclinic transformation (of about 200
nm), the tetragonal precipitates are retained
on cooling the material to room temperature.
The remaining Css phase does not get time to
transform.
 The PSZ microstructures are analogous to those formed
in precipitating metal systems.

 The optimum microstructures

contain about 25-30 vol.% of
tetragonal phase.
 Too much stabiliser tends to
generate grain boundary
precipitates, which are too
large to remain in the Tss phase.
 On the other hand, too little
stabiliser produces fewer Tss
phase and requires a higher
firing temperature.

Effect of CaO addition on firing temperature

and resultant microstructure.
 In over-aged microstructures, coherency is lost and particles spontaneously
transform to monoclinic phase on cooling.

 Twining also resulted, causing a decrease in transformation strain mismatch.

 Peak toughness in PSZ microstructure

is obtained when optimum mean
precipitate size is achieved, where the
optimum size is just below that for
spontaneous transformation.

 However, in the overaged state

microcrack toughening is possible and
so toughness falls away more slowly
than expected, Fig. 9.10.

Effect of ageing time on strength and

toughness of PSZ.
  Similar toughening procedures are used in the CaO-ZrO2
and Y2O3-ZrO2 systems.

Typical mechanical properties of different partially stabilised zirconia (PSZ).

Typical properties Mg-PSZ Ca-PSZ Y-PSZ

wt% stabiliser 2.5 – 3.6 3.0 – 4.5 5.0 – 10.0
Toughness, MPa m1/2 6 – 20 6 – 12 6–8
Modulus, GPa 170 – 210 200 – 220 180 – 220
Strength, MPa 440 – 720 400 – 650 650 – 1000
Tetragonal Zirconia Polycrystals (TZPs)

 These ceramics contain entirely of the tetragonal phase in

their structures.
 Y2O3-ZrO2 and CeO2-ZrO2 materials show this property.

Y2O3-ZrO2 system (Y-TZP)

 Very fine powders (<0.3 mm) containing about 2-3 mol% Y2O3 and 97-
98 mol% ZrO2 are densified completely in the TSS phase field at about
1400-1550 °C to produce a fine-grained microstructure consisting
almost entirely of tetragonal grains.

 Potentially 100 % of the microstructure is transformable near a crack

tip to inhibit crack propagation and resulting tougher ceramics.
ZrO2-Y2O3 binary phase diagram.
 The fracture toughness of Y-TZP can be very high,
 Toughness and the critical size of tetragonal crystals
depend upon the yttria content in the material

Variation in fracture toughness and critical grain size as function of yttria content
 A similar microstructure and properties can be achieved
in CeO2-ZrO2 system (Ce-TZP). Table 9.3 shows typical
properties of Y-TZP and Ce-TZP ceramics.

Typical mechanical properties of different tetragonal zirconia polycrystals (TZP).

Typical properties Y-TZP Ce-TZP

wt% stabiliser 2.0 – 3.0 12.0 – 15.0
Toughness, MPa m1/2 6 – 15 6 – 30
Modulus, GPa 140 – 200 200 – 220
Strength, MPa 800 – 1300 500 – 800
Transformation toughened zirconia: Advantages

 have great potential for wear resistant applications.

 can withstand more handling and in-service abuse that
conventional ceramics
 have coefficient of thermal expansions very similar to
those of cast irons, ranging from 9.5 – 11.0 x10-6 per deg C,
making them suitable to attach with metals
 Transformation toughened zirconia: Disadvantages

1. main drawback - decrease in strength and toughness with

increasing temperature.

 For toughening to occur, the tetragonal phase must be able to

transform into the monoclinic phase.

 However, the metastable tetragonal phase starts to become stable at

about 650 C and becomes completely stable at about 1150 C, so no
toughening occurs.

 Thus strength and toughness of transformation-toughened ceramics

have a progressive decrease in strength and toughness as the
temperature is increased.
(a) Strength and (b) toughness of transformed-toughened zirconia at different temperatures.
2. sensitive to thermal ageing

 Mg-PSZ and Ca-PSZ exhibit changes in precipitate size and grain size
at prolonged heating at about 1000 °C.
 This results in an increase in monoclinic phase and a decrease in tetragonal phase,
which subsequently decrease strength and toughness.
 1000-h ageing at 1000 °C causes a strength loss up to 30–70 % for of Mg-PSZ, and
only about 7 % for Y-TZP.
 This shows Y-TZP has a better high temperature property.

 Exposure of Y-TZP to 300 °C for about 500 h causes a drop of strength

from 900 to only 250 MPa, showing its unstability at low
temperatures.
 This has occurred due to conversion of tetragonal phases to monoclinic phases
during low temperature ageing.
 This conversion was found to be enhanced by the presence of water vapour, coarser
grain, and Al2O3 content.
Zirconia – toughened Ceramics (ZTCs)

 These materials consist of tetragonal or monoclinic zirconia

particles finely dispersed in their structures
 increase their strength and toughness by transformation toughening

 Especially good results have been obtained with materials

having Al2O3 as the matrix (e.g., alumina, mullite, spinnel).
Zirconia toughened alumina (ZTA)

Increased strength and toughness

16 vol.% ZrO2 addition produces strength >1000 MPa; toughness >10 MPa.m1/2

Increased thermal shock damage and slow crack growth

resistance
Pure alumina – T for thermal-shock damage = 300 °C
14 vol.% ZrO2 – about 700 to 900 °C

Pure alumina – strength dropped from 320 to less than 150 MPa
14 vol.% ZrO2 – from 700 to about 500 MPa