C hemical & M aterials

ENGINEERING

School of Engineering

University of Auckland

Properties of Matter

CERAMIC MATERIALS M. Hodgson (Rm. Eng 1.603 ) Notes by: Dr Necati Ozkan
OUTLINE
(1) Introduction (Recommended reading: Smith Session 10.1) (2) Ceramic Crystal Structures (Recommended reading: Smith, Session 10.2) (3) Silicate Structures (Recommended reading: Smith, Session 10.3) (4) Glasses (Recommended reading: Smith, Session 10.9) (5) Thermal Properties (Recommended reading, Smith, Session 10.8) (6) Mechanical Properties (Recommended reading: Smith, Session 10.7) (7) Processing of Ceramics (Recommended reading, Smith Session 10.4)

1. INTRODUCTION
Ceramic materials are inorganic compounds consisting of metallic and nonmetallic elements which are held together with ionic and/or covalent bonds. IONIC BONDING
Valence Electron

Na+ Ion Cl Atom Na Atom Cl - Ion

COVALENT BONDING
-

+
--

Covalent Bonds

+
Silicon Atom

+
-

+
--

+
-

Strength of Bonds
STRONG WEAK SECONDARY BONDS

COVALENT

IONIC

METALLIC

THE DEGREE OF IONIC CHARACTER The degree of ionic character of a ceramic compound can be estimated approximately using the following formula: % Ionic Character = { 1 - exp[-0.25(XA-XB )2]} x 100 XA = Electronegativity of element A XB = Electronegativity of element B

2. STRUCTURE OF CERAMICS
REVIEW OF CRYSTALOGRAPHY

Number of Atoms per Unit Cell

When counting the number of lattice points belonging to each unit cell, we must recognize that lattice points may be shared more than one unit cell. The atom located at a corner of one unit cell

The atom located at an edge of one unit cell

The atom located at a face of one unit cell

The atom located at the center (inside) of one unit cell

Atomic Radius versus Lattice Parameter

Simple Cubic Face Centered Cubic Body Centered Cubic

r r r r a 2r

r 2r r

a = 2r

2 a = 4r a= 4 r 2

3 a = 4r a= 4 r 3

INTERSTITIAL SITES
TETRAHEDRAL SITES IN FCC STRUCTURE

OCTAHEDRAL SITES IN FCC STRUCTURE

SIMPLE IONIC CERAMIC STRUCTURES

Factors which influence the crystal structures: (i) Electrical charges on the ions needed to be balanced.

(ii) Relative sizes of ions: Radius Ratio = rc /ra COORDINATION NUMBERS (CN): the number of anion nearest neighbours for a cation is related to cation/anion radius ratio. (The most common CNs are 4, 6, and 8).

NOT STABLE

STABLE

STABLE

0.155 < rc /ra< 0.225 0.225 < rc /ra< 0.414 0.414 < rc /ra< 0.732 0.732 < rc /ra< 1.0

CN = 3 CN = 4 CN = 6 CN = 8

(iii) Ions tend to be packed together as densely as possibly to lower the overall energy of the solid.

SODIUM CHLORIDE STRUCTURE

FLUORITE (CaF2 )STRUCTURE

F-

Ca++

ao

ao

ALUMINA (Al2O3)

O -2 Al +3

COVALENT STRUCTURES
ZINC BLENDE (ZnS) STRUCTURE (BeO, SiC)

C Si

, S-2 , Zn +2

Tetrahedral cube
PEROVSKITE STRUCTURE
BaTiO3 is a perovskite type structure. Above 120 oC, the unit cell is cubic, with each Ti 4+ ion octahedrally coordinated among six neighbouring oxygen ions.

Ti 4+ Ba 2+ O 2-

(r = 0.068 nm) (r = 0.134 nm) (r = 0.132 nm)

3. SILICATE STRUCTURES
The silicate structures are based on the silica tetrahedra (SiO44-).
Silica tetrahedra

Silica tetrahedra behave as ionic groups.

Double Tetrahedron

Ring and Chain Structures

Sheet (Layer) Structures

Silica Structure SiO2

Crystalline

Amorphous

4. GLASSES
Non-crystalline or amorphous structure developed from SiO4-4 tetrahedra. Most inorganic glasses are based on silica ( SiO2 ).
TABLE: Typical composition(wt %) of some of the common commercial glasses. Glass Fused Silica Pyrex Glass Jars Window glass SiO2 99 81 74 72 Al2O3 2 1 1 CaO Na2O 4 15 14 B 2 O3 12 4 2 MgO

5 10

General Characteristics of glasses (i) Short range atomic order but no long-range order (ii) Structure is isotropic, so the properties are uniform in all directions (iv) Typically good electrical and thermal insulators (v) Soften before melting, so they can be formed easily by various forming techniques. GLASS NETWORK MODIFIERS: Most silicate glasses contain Network Modifiers. Network modifiers are oxides such as Na2O and CaO which supply cations (positive ions) to the structure. The addition of Na2O to a silica glass introduces two Na+ ions, and produces two nonbridging oxygens (i.e. induces oxygen bridge failure).

Na+ + Na2O Na+

Glass Transition Temperature

Specific Volume

Shrinkage due to solidification

Tg
Viscosity of Glasses

Tm

Temperature

(Viscosity is the resistance of a liquid to deformation by shear). Above Tg, a glass behaves as a viscous liquid.

16 log (viscosity), Pa.s 14 12 10 8 6 4 2 working point Temperature softening point strain point annealing point

5. THERMAL PROPERTIES OF CERAMICS and GLASSES

Many ceramic applications result directly from the high melting temperature of some ceramic materials. High melting temperature is a result of high bond strength. Bond energy is proportional to the MELTING TEMPERATURE. Due to their strong ionic - covalent bonding, most ceramics have low thermal conductivities and thermal expansion coefficients.

THERMAL SHOCK Thermal shock refers to the thermal stresses that occur in a component as a result of exposure to a temperature difference between the surface and interior or between various regions of the component. The peak stress typically occurs at the surface during cooling according to the following equation: T = ( E T ) / (1-) When selecting a ceramic material for an application where thermal shock is expected to be a problem, calculation of the appropriate thermal shock parameter (R) (or the maximum allowable temperature difference, Tmax ) for various candidate materials may be useful.

6. MECHANICAL PROPERTIES OF CERAMICS

(i) Hard and strong, (ii) Good wear resistance, (iii) Brittle, low toughness and ductility, and (v) Good high temperature mechanical properties. Theoretical strength of material is proportional to (E/10). Since the value of E (elastic modulus) is very high for ceramics. There is a potential for obtaining very strong ceramics. However, the limitation is the DEFECTS. Example: ALUMINA
E = 380 GPa Estimated theoretical strength = 38 GPa Measured strength of polycrystalline sample = 0.4 GPa Measured strength of fibers = 16 GPa

Stress Concentration
F A

2a

ct Stress at the crack tip

A (applied pressure) = F/A

The stress intensity at the crack tip depends on (i) the applied pressure, (ii) the size of the crack, and (iii) the geometry of the crack. The stress intensity factor (KI) is given by : KI = Y A ( a )1/2

Fracture Toughness (Critical intensity Factor) Critical value of KI that causes failure is called the critical intensity factor (KIC) or the fracture toughness. KIC = Y f ( a )1/2 where f = fracture stress (strength) Materials that show little plastic deformation before fracture will have lower values of KIC .

IMPROVING FRACTURE STRENGTH OF CERAMICS

K IC = Y f a f = K IC Y a

1. Reduce The Size Of Cracks (Defects)

Defect size can be reduced by optimising processing steps and by using good quality ceramic powders (uniform and small particle size, pure, unagglomerated, and equiaxed particles)

2. Increase KIC (i) Transformation Toughening (Partially stabilised ZrO2 (PSZ))

Tetragonal ZrO2 grain Monoclinic ZrO2 grain Cubic Matrix

(ii) Formation of Microcracks.

Microcrack

(iii) Fiber reinforced ceramics

MEASUREMENT OF MECHANICAL PROPERTIES OF CERAMICS TENSILE TEST

F

Tensile strength = =
y x L c d w c z x

Load F = Area A

K IC =

YF f wd

BENDING TESTS Three point bending test

F b h
F/2 F/2 Bending moment diagram FL/4

L/2

L/2
3F f L 2 bh 2

Modulus of Rupture ( Maximum stress at fracture ) = mr RECTANGULAR : mr = CIRCULAR : mr = F f = load at fracture L = dis tan ce between sup port po int s Ff L R3

7. PROCESSING OF CERAMICS

Ceramics are manufactured by using POWDER FORMING TECHNIQUES.

PROCESSING ADDITIVES

POWDER PRECURSOR PREPARATION

PRECURSOR (Agglomerates (granules), Suspensions, Pastes)

FORMING (Pressing, Slip Casting, Extrusion)

GREEN COMPACT

DRYING BINDER BURNOUT SINTERING (FIRING) FINAL PRODUCT

CERAMIC MANUFACTURING TECHNIQUES

U n iaxial Die Pressing

DIE PRESSING
PUNCH

The die pressing is accomplished by placing the powder into a die and applying pressure to achieve a desired level of compaction. PRODUCTS: Insulating, dielectric, and magnetic ceramics for electrical devices; Substrates, Capacitors

D IE POWDER (Agglomerated)

SLIP CASTING

Suspension (Slip)

Porous Mould

The main step for slip casting are: (i) Preparation of a stable suspension (slip). Suspensions are prepared by mixing ceramic powders and processing additives (binders, dispersing agents) with a liquid (water or solvent). (ii) Pouring the slip into a porous mold (plaster of Paris). (iii) When a sufficient wall thickness is formed, the excess slip is poured out of the porous mold. (iv) The cast material is allowed to dry in the mold and subsequently the dried product is removed from the mold. (v) The dried product is fired (sintered) to obtain dense final product.

EXTRUSION
The ceramic paste is placed in an evacuated cylinder, the paste is then forced through a die. As the shaped ceramic paste exists from the extruder, it is supported on a suitable flat or shapes surface to prevent distortion and cut to the required lengths. Examples : Furnace tubes, Resistance heaters, Magnets, Heat-exchanger tubes.

PISTON BARREL CERAMIC PASTE

DIE DIE RESTRAINT

PRODUCT

DRYING
Drying is the removal of liquid from a green ceramic body. Drying must be carefully controlled, stresses produced by differential shrinkage or gas pressure may cause defects in the green ceramic body.

BINDER BURNOUT
Binder burnout is the removal of processing additives (binders, plasticisers, dipersants) from a green ceramic body.

SINTERING
Sintering is the final stage of ceramic processing in which porous powder compacts are converted to the dense material. The driving force for the mass transport during the sintering process is the reduction of the free energy of system (The decrease in surface area and lowering of the surface free energy by the elimination of solid-vapour interfaces). The driving force usually takes place with the formation of new, but lower energy, solid-solid interfaces The driving force for sintering can be expressed generally as follows:

F = sv Asv + ss ass

L Lo

Lb Lob

General Sintering Rate Equation

d Q 1 = A exp s RT G n dt = density A , n = constants Q s = activatio n energy f or sinterin g G = particle (or grain) size

Shrinkage During Sintering

Sintering Lg Green Compact Ls

Sintered Compact

GRAIN GROWTH The driving force of the grain growth process is the difference in energy between the fine - grained material and the larger grain size product resulting from the decrease in grain boundary area and total boundary energy.

t1 t1 < t2 < t3

t2

t3