MME 467

Ceramics for Advanced Applications

Lecture 24
Examples of Toughened
Ceramics 2
Ref: Richerson, Modern Ceramic Engineering, Ch17, Marcel Dekker, 1992
Topics to discuss....

1. Particle-reinforced ceramics
2. Whisker-reinforced ceramics
3. Fibre-reinforced ceramics
 Particle-Reinforced Ceramics

Toughening in particle-reinforced ceramics is achieved by:

1. Crack deflection
In cases when particles do not react with the matrix

2. Crack bridging
When the particles are irregular in shape with higher aspect ratio,
or have grain sizes much larger than that of the matrix

3. Microcrack toughening
If the particles have a significantly different coefficient of thermal
expansion than that of the matrix
 The presence of non-reactive second phase generally
inhibits complete densification and formation of finer
grains, unless a liquid phase is present

 In presence of a liquid
phase full densification
can be achieved by hot
pressing or hot-isostatic
pressing (HIPping), and in
some cases conventional
sintering.

Photomicrograph of a pressureless sintered post HIPed

Al2O3 – 30 wt% TiC particulate composites
Example of particulate-reinforced ceramics
 Whisker-Reinforced Ceramics

Whiskers

 single crystals, grown preferentially along a specific crystal

axis and have typical ranges from about 0.5-10 mm in
diameter and a few microns to a few centimetre in length

 have a very high strength (~ 20 GPa) due to the presence of

small processing defects such as voids, inclusions, and
surface roughness

Hazardous, should be handled with care

Comparison of properties of some whiskers and matrix materials
 The whiskers are fully dense and rigid, so they do not shrink
during sintering.
 they inhibit matrix material transport necessary for sintering to reach
completion
 in most cases, hot pressing has been required to achieve a near-
theoretical density of the matrix

 The reorientation of the whiskers during hot pressing forces

the matrix material to move large enough distances to
permit full densification.
 produces a microstructure where many of the whiskers align along the
perpendicular direction of hot pressing
 results in anisotropy in strength and toughness of material

 Conventional liquid-phase sintering can also produce an

increased randomness of whisker orientation, but with a
decrease in strength and toughness.
Example of whisker-reinforced ceramics
Alumina Composites
Reinforced with SiC Whiskers

 Substantial improvement in properties can be achieved in

alumina with SiC whisker reinforcement.
 toughness is almost doubled and the strength increased by over 50 %
 improvements persist to elevated temperatures

Variation in strength with

temperature of hot-pressed
SiC whiskers reinforced
alumina composites.
 SiC whiskers reinforced alumina also showed improved
thermal shock resistance, high Weibull modulus, and low
creep rate.

Material Thermal Shock Resistance

Pure alumina Severe drop in strength during quenching

from above 200 ºC
Alumina + SiC whiskers Survive quenching from above 900 ºC

Material Weibull Modulus

Pure alumina 4.6

Alumina + 15 % SiC whiskers 13.4
Alumina + 25 % SiC whishers 22.5
 Differences in whisker
characteristics (surface
chemistry, presence of defects,
etc.) have pronounced effect on
processing and properties of
composites.

Surface chemistry
 affects the degree of dispersion of whiskers
in the matrix
 the interface bonding between the whiskers
and the matrix
 influences the degree of whiskers pullout,
bridging, and stress delocalisation

Defects
 consists of different levels of inclusions,
voids, or other defects SiC whiskers with
various sizes and
 limit the strength of whiskers and the smoothness
material in general
Examples of components fabricated of Al2O3 – SiC whiskers composites
MoSi2 and MoSi2-WSi Composites
Reinforced with SiC Whiskers

 Molybdenum disilicide (m.p. ~ 2030 C)

 intermetallic compound having excellent oxidation resistance
 heating element for HT furnaces (>1700 C in air)

 Two primary problems hindering its structural applications:

1. low toughness at low temperature, and
2. high creep rate at elevated temperature

 The source of both types of behaviour is its ductile-to-brittle

transition at about 1000 C.
 Below 1000 ºC, the material is brittle with low toughness 5.3 MPa m1/2.
 Above this transition, MoSi2 becomes increasingly ductile.
 For example, the yield stress of MoSi2 at 1200 C is about 139 MPa,
which decreases to 19 and 8 MPa at 1400 and 1500 C, respectively.
 Reinforcement with SiC whiskers increases both toughness
and strength of MoSi2.

Properties of SiC whisker-reinforced MoSi2 ceramics

 Fibre-Reinforced Ceramics

 Reinforcing ceramics with dispersion of particles or

whiskers can increase toughness and strength of ceramics.
 this results in a material of increased reliability and reduced flaw size
 strain-to-fracture is still about the same as for a monolithic ceramic
 the material continues to fracture in a brittle, catastrophic mode

 Reinforcing with a fibre increases the distance over

which a toughening mechanism can act and leads to
enough strain-to-fracture so that the fracture is no longer
catastrophic.
 Fibres that are used for ceramic reinforcing can be either
 single strand (monofilament) or multifilament strand
 amorphous or polycrystalline with very small grain size (~ nm)

 Common manufacturing processes:

 Drawing a molten glass/polymer/viscous gel through a smooth die
 Chemical vapour deposition onto a smooth carbon fibre
 Conversion of a carbon fibre into SiC fibre

 Defect size in fibres is very small resulting high strength.

 Common fibres used for ceramic reinforcement:

glass fibre, carbon fibre, SiC fibre, Si-C-N fibre
Glass fibres
 Low elastic modulus
 Not suitable for reinforcing most ceramic materials

Carbon and graphite fibres

 Have wide range of properties:
D = 1.7 – 2.0 g/cc, E = 200 – >500 GPa, TS = <1500 – >5000 MPa
 Mechanical properties limited to moderate temperatures (<300 ºC) due to
poor oxidation resistance

SiC fibres
 Much higher temperature capability
 Many SiC fibres are not pure, instead are a mixture of C, SiO2, and SiC.
SiO2 and C contents are greatest at the surface and decrease inward
 These impurities affect interfacial bonding with the matrix and thermal stability
 Fibre strength degraded above 1200 ºC
Typical properties of ceramic fibres
Glass Matrix Composites

 Discontinuous C fibre reinforced glass matrix composites

are usually prepared by tape casting methods followed by
hot pressing
 viscous behaviour of glass at hot-pressed temperature (1150 ºC)
allows enough mobility of the matrix to achieve full density under
moderate pressures without damaging the fibres

 Densification at low-enough temperature without chemical

degradation or formation of strong bond with the matrix
 substantial increase in toughness resulted

 Example: Toughness of Pyrex glass

Pure Pyrex glass < 20 J/m2
Pyrex + 10 vol% C-fibre 125
Pyrex + 20 vol% C-fibre 280
Pyrex + 30 vol% C-fibre 460
  The stability of glass composites is decreased with
increasing temperature in an oxidising atmosphere.
 strength of C fibre reinforced borosilicate glass over 600 MPa
is maintained up to 600 C.
 strength of un-reinforced glass falls below 100 MPa

Effect of temperature
on flexural strength of
carbon fibre-reinforced
glass composite

 Thus, C fibre-glass composites have limited use at HT.

 Use of SiC fibres in borosilicate and other high silica glass
matrices results in strength versus temperature curves
similar in shape to the one shown earlier but displaced
vertically to slightly higher strength.

 The stability of composites in oxidising atmosphere

improves substantially in the ranges of 500 to 600 C.

 SiC fibre reinforced glass composites showed no strength

reduction even after 500-h exposure at 540 C.
Glass-Ceramic Matrix Composites

 Two limiting factors of glass-matrix composites:

(1) softening of the glass above 600 C, and
(2) oxidation at low temperatures.

 Glass ceramic systems (lithium aluminosilicate, LAS)

were developed to improve the high temperature capability
of the matrix.
 formed as a glass and then heat treated to develop a fine-grained
crystalline microstructure
 Like pure glass, crystalline glass does not exhibit softening behaviour
 Earlier TiO2 added LAS glass composites produced low
strength and toughness and fractured in a brittle manner.
 The matrix and the fibre interacted during hot pressing to produce
strong interfacial bonding.
 Cracks were not deflected by the fibres and no crack bridging or
pullout was occurred, leading to the brittle fracture behaviour.
 TiO2 added to LAS as a nucleating agent was judged to contribute
this strong interfacial bonding.

 A combination of ZrO2 and Nb2O5 additions produce weak

interfacial bonding and, thus, excellent composite behaviour
with high strength and toughness.
 A thin layer of NbC developed at the fibre-matrix interface was
determined to be the source of this weak bonding.
 The LAS with of ZrO2 and Nb2O5 additions was referred to as LAS III
composites.
 Strength, toughness and
temperature capabilities are
increased dramatically compared
to unreinforced or monolithic
LAS.

Samples tested in air exhibited

approximately 25 % lower
strength at 700 C and 50 %
lower strength at 1000 C
compared to argon testing.

This can be correlated with a 20-

fold increase in interfacial bond
strength at 1000 C compared to
room temperature.

Flexural strength and toughness of SiC fibre

reinforced LAS III composites.
 Fracture surface of continuous-fibre reinforced ceramic matrix composites.
(a) X15, (b) X500.

 The high degree of fibre pullout indicates the presence

of debonding, pullout, and bridging of fibres consistent
with high composite toughness