Ceramic Science 4RO3

Lecture 6 October 28, 2013

Tannaz Javadi
 Strength and toughness
Brittle fracture
Theoretical strength (σth): the stress necessary to separate a body into
two part simultaneously across the cross section.

Forming new surfaces (2ɣ)

Surface energy (ɣ)
The equilibrium spacing (a0)
Modulus of elasticity (E)

The observed strength of brittle materials are often much less than that predicted

Initiation and propagation of flaw

(Griffith theory)
 Brittle fracture
Griffith:
• suggested that the flaws in the materials act as stress concentrators
• a crack propagates when the decrease in stored elastic energy
associated with its extension exceeds the increase in surface energy
created

Gc: Energy needed to expand the crack

(Gc is the surface energy per unit area
of crack, J/m2).

C: elliptical internal crack size

For brittle materials: Gc=2ɣ

 Stress Intensity Factor and Fracture Toughness

• An applied stress is amplified at the tip of a crack

• Stress intensity factor (K): a measure of the degree to which
an external stress is amplified at the tip of a crack, depends
on:
o shape of the crack
o manner in which it is loaded
o not on the specific material
• Critical Stress Intensity Factor (kc): Fracture toughness
the externally applied stress is increase to reach a critical
energy release rate (Gc) causing an unstable crack to
propagate
o highly material dependent
 Fracture toughness
• lower limit to the fracture toughness is for purely brittle materials
that the only resistance to crack propagation is the surface energy
• For not purely brittle materials the energy required to propagate
crack exceeds that given by surface energy alone.

develop ceramic microstructure (increase the energy absorption

during crack propagation)

Typical values of the fracture toughness for ceramics:

Materials Fracture toughness Reason
Glasses & Single crystals 0.5-2 Mpa.m1/2 Easy cleavage planes
Polycrystals (Sapphire) 2-5 Mpa.m1/2 More tortuous crack
path with greater
fracture surface energy
Toughened ceramics 6-12 Mpa.m1/2 Energy absorbing
microstructure
 Strengthened Ceramics
Surface Flaws are the most dangerous flaws in most ceramic
bodies

In order to improve fracture strength of ceramic:

1- avoid development of surface flaws (i. e. Polishing)

2- develop surface compressive stresses (counteract the flaws)

o Thermal tempering (Air jet cooling)
o Chemical treatment (exchange of large K for Na in glasses)
o Use a laminated structure (a low thermal exp. coeff. layer
on a greater thermal exp. underlying glass via diffusion)
 Microstructural Toughening
Fracture toughness for common structural metals > 30 Mpa. m1/2

Extensive plastic work and crack blunting during fracture

The fracture toughness and strength of polycrystalline ceramics
improved by controlling their microstructure
Silicon nitride: 1 GPa strength, 6-10 Mpa. m1/2
Partially stabilized zirconia (PSZ) and tetragonal zirconia polycrystals
(TZP): 0.6-1 GPa, 6-10 Mpa. m1/2
Ductile metal-toughened ceramics: 10-15 Mpa. m1/2
Applications:
SiN for Automotive components: turbocharger rotors, high temperature
gas turbines
Fiber reinforced ceramics and glasses: jet engine comp., cutting tools
 Microstructural Toughening
To increase both strength and toughness in brittle materials
• Decrease the characteristic flaw size
Careful processing
• Narrow the distribution in flaw size
Microstructural toughening: the resistance to crack growth is not a
constant, but increases as a flaw propagates (flaw tolerance)

 Reliability increases since smaller flaws can grow to a limiting size

before failure and the initial distribution of flaw sizes becomes less
important.
Sometimes an increase in fracture toughness happens at the expense of
strength
o Coarse grained porous firebrick
o Polycrystalline aluminum titanate
These ceramics derive high thermal shock resistance from extensive
microcracking

They are relatively tough but relatively weak ceramics

 Transformation-Toughened Zirconia
 Partially stabilized zirconia containing fine plate-like precipitates of
the metastable tetragonal phase

 Three different sorts of toughening (ENERGY ABSORPTION)

o Transformation from tetragonal to monoclinic happens at the tip

of the crack due to the intensified stress, (energy absorbed and
volume expansive strain produce)

o Additional energy absorption comes from the local stress fields

around the transformed particles (microcracks develop in the
intensified stress field) (decrease the effective stress intensity at the
crack tip)
o Crack deflection caused by localized residual stress fields (forms
due to transformation), increase crack surface area and effective
surface energy and therefore toughened the material.
 Transformation-Toughened Zirconia
•stress induced transformation in the course of load
•initiation of fine cracks
•deviation of cracks from their initial direction of growth


Schematic representation of the effects related to the dissipation
of energy at crack growth in metallic and ceramic matrices
Physical and Metallurgical Characteristics of Fiber Reinforced Ceramic Matrix Composites, Zdeněk, et.al, VŠB-Technical University of Ostrava, Czech Republic
Energy absorption process:
R-Curve
• At the beginning only a front zone is
affected

• As the crack propagates, a larger

zone is affected.

• finally the process zone fully

developed and reached a steady
state

• the crack resistance is increased by

an amount ΔKR.

The R-Curve describes the

Predicted crack resistance for T-T showing
crack resistance as a function an approach to a limiting Kc as the crack
of crack extension, KR (Δc). extends.
 R-Curve and Fracture
• The applied stress intensity (KI) varies
parabolically with crack length, KI α σc1/2

• By increasing the applied stress KIC is

reached at smaller crack length.

• Brittle materials have constant fracture

toughness, (flat R-Curve) and Griffith
fracture happens when the applied KI
reaches KIC.

• Tough materials (rising R-Curve), the

crack resistance KR, increases beyond its
initial value along the heavy line →
 R-Curve and Fracture

• If the crack resistance (KR) rises faster with

crack extension than the amplified stress near
the crack tip (KI):

The crack can extend stably without failure

occurring.

• Eventually the R-Curve flattens, and crack

resistance cannot keep up with the applied KI .
The point of tangency between the two curves
shown defines the failure criterion.
 Crack Bridging
Any microstructure (Ligaments, Fibers, Ductile particles) that bridge the
crack after the crack front has passed toughened the material.

• taking up some of the stress tending to open the crack and decrease
the intensity of the stress at the tip of the crack.

• fiber-reinforced ceramics
• ductile metal-phase-toughened ceramics
• polycrystalline ceramics with large, anisotropic grains
 Crack Deflections
The greater toughness of polycrystalline ceramics, Whisker and particle
reinforced ceramics compared to single crystal ceramics is due to:

• Bridging
• Crack deflection around grain boundaries/ interfaces
o Stress intensity factor decreases at the tip of a deflected crack
o increasing volume fraction of deflection materials
o increasing their aspect ratio (not size)
 Example: Si3N4

In-situ formed composite, rodlike β-phase of Si3N4

 Ceramic Processing
Gas-Phase Reaction

• Chemical Vapor Deposition (CVD)

o Films, monolithic bodies
o Endothermic reaction
o Electronic devices films
o Composites
o Coatings
o Si3N4: SiCl4 + NH3

• Directed Metal Oxidation

o Reaction btw gas/liquid
o Composites (Oxides, Nitrides, Borides,...)
o Porous and dense body

• Reaction Bonding
o Reaction btw gas/solid
o SiC and Si3N4 bodies
o Machined silicon shaped body subjected to N2 gas, high porosity Si3N4 forms
o little shrinkage (high degree of dimensional accuracy)
 Ceramic Processing
Liquid Precursor Methods: solid body
formed out of a solution of metal
compounds
• Sol-Gel Processing
o Solution of metal compound/
Suspension of very fine particles
in liquid (Sol) is converted to
semirigid mass (gel)
o high purity materials
o high amount of shrinkage
o suitable for small and thin
films, fibers, powders.
• Polymer Pyrolysis
o polymerization reaction in
liquid solution
o Considerable shrinkage
o SiC fibers
 Ceramic Processing
Fabrication from Powders: (most widely used method)
• Melt Casting
o melting a batch of powdered raw materials, followed by
cooling and forming to a solid finish body
o nucleation & growth
o uncontrolled grain growth
o high melting point or decompose before melting
o glasses, glass-ceramics
• Firing of Compacted Powders
o Consolidation a mass of fine
powder to a porous form
(green body), then fired to a
dense product
 Powder processing
1. powder production,
2. preparation of powders for consolidation,
3. consolidation to an engineering shape
4. removal of solvent and organic additives (drying and burnout),
5. densification.
Properties of the green body

1. a high, uniform packing fraction of particles,

2. small and narrow size pores,
3. a high degree of homogeneity (sintering additives and reinforcing
phases being well mixed).
4. common heterogeneities such as agglomerates, organic inclusions
and gas bubbles, have to be avoided.
5. decrease the size of the powders (typically <1 µm) to enhance
sinterability at lower temperatures.
 Powder preparation and characterization
Characteristics of the powder depends on the method of its preparation

1. Size
2. Size distribution
Powder characteristics 3. Shape
4. Degree of agglomeration
5. Chemical composition
6. Purity

1. Mechanical methods (grinding, milling)

Powder preparation

1. Chemical methods (chemical reaction)

 Powder preparation and characterization
Powders characteristic:
• homogeneous chemical composition
• Purity of the powders during processing
• preparation of fine powders (more surface area, high
activity, high density bodies, low firing temperature
o Formation of agglomerates (non-uniform
consolidated powder) (deleterious effect)

Materials Particle size Density Temperature

CeO2 10-20 nm Full density 1100 °C
CeO2 1𝜇m Low density 1600 °C
 Powder Consolidation
1. Dry or semidry pressing of the powder in a die
2. Mixing the powder with water or organic polymers (pressing plastic
mass): plastic forming
3. Casting from slurry (slip casting, tape casting)

Homogeneous packing density in green body plays an important role in

the subsequent firing stage and optimising final properties of the
ceramic body

Colloidal technique
 Colloidal technique
Continuous phase (dispersion medium), liquid/gas

Colloid
Fine dispersed particulate phase (solid/liquid)-1-1000 nm

Advantage:
•Better packing uniformity in the green body
•Better microstructural control during firing

Stability of colloidal suspension

Not too large particles-----gravity and sedimentation

Not too large attractive van der waals force-----
flocculation/coagulation
Introduction of repulsive force (electrosteric stabilization)
 New terms
Colloids
• solid particles in a liquid (sol or colloidal suspension, e. g. Paint)
• liquid particles in a liquid (emulsion, e. g. Milk)
• liquid particles in a gas (aerosol, e. g fog)

Repulsive forces
• between electrostatic charges (electrostatic stabilization)
• between polymer molecules (polymeric stabilization)
• combination of the two (electrosteric stabilization)

Electrophoresis: the motion of the particles in an electric field

Rheological properties: deformation and flow properties of the

colloidal suspensions
 Colloidal stable system

 Introducing an interparticle repulsion

Creating an electrostatic double layer at the
solid/liquid interface
2 methods of stability

Adsorbing polymers or surfactants on the

particles surface

Electrostatic double-layer forces

• Charge build up at the solid–liquid interface of ceramic powder
which is immersed in a polar liquid (e.g. Water)
The most common way:
• The interfacial charge is a result of adsorption or desorption of
ionic species in solution.
 Adsorption of ions from solution
• Acid, Base or metal salt is added to the solution
• Ions preferentially adsorb onto the surface of particles
and charge on the particles form
• to be electrically neutral, an equal and opposite counter
charge exists in the solution.
Positively charged surface at low pH

PZC
•Point of zero charge
•Intermediate pH
•H+ will balance OH- ions
•Neutral particle surface
•Low PZC for acidic oxides
•High PZC for basic oxides
Most oxide
surfaces are
hydrated Negatively charged surface at high pH
(MOH)
 Zeta Potential (ƺ)
The potential deference between the slipping plane versus a point in
the bulk fluid away from the interface.

• IEP: the pH where the ƺ

potential is zero is called
isoelectric point.

Stable colloidal suspension

The diffuse double layers of

two adjacent particles start
to overlap and increase the
repulsion between them
 Stable colloidal suspension
Deflocculation
A:
•The repulsion is weak
• The particles attract each other and reach
equilibrium at M1
• A sediment consist of clusters of particles
produced (Coagulation)

B:
• The repulsion increased and M2 forms
(chance for flocculation)
• the height of the maximum at P1 is
comparable to kT
•Particle overcome the P1 and fall into the
M1
•Irreversible coagulation will form
 Stable colloidal suspension
Deflocculation
C:
• The double layer repulsion become so
large, no M2 forms
• Hight of P1 is much greater then kT, no
chance of surmounting the energy
barrier
• Represents the situation for a stable
colloid

D:
• Attraction is much smaller than repulsion,
no minimum in the curve
• Extremely stable colloid
• limits the concentration of particles in
suspension
 Deagglomeration and dispersion of ceramic powder
• the agglomerates, present in most starting powders, either have to
be broken down or removed.
• primary particles, typically of a size between 0.5 and 1 µm, are small
agglomerates.
• It is necessary to break down both the secondary agglomerates (50 -
200 µm) and the primary agglomerates.
• the interparticle bonds can be dissolved (shifting pH away from the
stable region and increasing T) or broken by excessive mechanical
forces.