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Ceramic Materials Structures and Mechanical Properties

Prepared by Dr. Ang Bee Chin

Issues to Address
Structures of ceramic materials: How do they differ from those of metals? Point defects: How are they different from those in metals? Impurities: How are they accommodated in the lattice and how do they affect properties? Mechanical Properties: What special provisions/tests are made for ceramic materials?

Prepared by Dr. Ang Bee Chin

Introduction
Ceramic materials Inorganic, compounds between metallic and non-metallic elements Bonded by ionic or covalent bond or combination of two Relatively stiff and strong, very hard and extremely brittle More resistant to high temperature and harsh environments than metals or polymers Examples: aluminum oxide (Al2O3), silicon dioxide (SiO2), silicon carbide (SiC), silicon nitride (Si3N4), clay minerals, cement, glass

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Introduction
Common objects made of ceramic materials

Building brick

Cup

Glass vase

Scissors

Floor tile

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Introduction
Ceramics used for engineering applications can be divided into two groups

Traditional ceramics: primary raw material is clay Example: porcelain, bricks, tiles, glasses Engineering ceramics: consist of pure or nearly pure compounds Example: aluminum oxide (Al2O3), silicon carbide (SiC), silicon nitride (Si3N4)

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Ceramic Bonding
Bonding: -- Mostly ionic, some covalent. -- % ionic character increases with difference in electronegativity. Large vs small ionic bond character: CaF2: large
SiC: small

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Ceramic Bonding
Atomic bonding ranges from purely ionic to totally covalent

Many ceramics have combination of ionic and covalent bonds The percentage ionic character (%IC) depends on the difference in electronegativity
The greater the difference, the more ionic the bond, %IC can be predicted using Paulings equation % IC =
-0.25 (XA-XB)2 1-e

x 100%

XA and XB are the electronegativities for the respective elements


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Ionic and Covalent Bonding in Simple Ceramics

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Example

Calculate the ionic percentage of SiC (XSi = 1.8 and XC = 2.5).

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Crystal Structures
More complex than those of metals since ceramics are composed of at least two elements Crystal structures may be thought of as being composed of electrically charged ions (cations and anions) instead of atoms Ionic solids tend to have their ions packed together as densely as possible to lower the overall energy. Cation prefers to have as many as possible nearest-neighbor anions and vice versa

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Crystal structure is influenced by the packing of ions and the packing of ions depends by two characteristics of ions: 1. Magnitude of electrical charge The crystal must be electrically neutral 2. Relative sizes of the cations and anions Cations (give up electron) are ordinarily smaller than anions (receive electron).

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Ionic Bonding & Structure


1. Size - Stable structures: --maximize the # of nearest oppositely charged neighbors. + + + -

unstable

stable

stable

If the anion does not touch the cation, then the arrangement is unstable.

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Ionic Bonding & Structure


Stable ceramic crystal structures form when anions surrounding a cation are all in contact with that cation

The number of anion nearest neighbors for a cation (coordination number) is related to the cation-anion radius ratio (rC/rA)
For a specific coordination number, there is a critical or minimum ratio (rC/rA)min for which this cation-anion contact is established (purely geometrical considerations) Critical radius ratio for stability for coordination numbers 8,6 and 3 are >0.732, >0.414 and > 0.155 respectively.

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Ionic Bonding & Structure


2. Charge Neutrality: --Net charge in the structure should be zero.

--General form:
FCa 2+ cation

CaF 2 :

anions
F-

A m Xp
m, p determined by charge neutrality

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Crystal Structures
Anion locations Two sides

Corners of equilateral triangle


Corners of tetrahedron

Corners of octahedron

Corners of cube

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Example

1. Calculate the critical (minimum) cation-anion radius ratio (rC/rA)min for the coordination number 3 2. Determine minimum rcation/ranion for OH site (C.N. = 6)

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Example
3. On the basis of ionic radii, what crystal structure would you predict for FeO?
Cation
Al 3+ Fe 2 + Fe 3+ Ca 2+

Ionic radius (nm)


0.053 0.077 0.069 0.100

Anion O 2Cl F17

0.140 0.181 0.133


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Types of Crystal Structures

AX-type crystal structures Equal numbers of cations and anions Sodium chloride (NaCl) structure Cesium chloride (CsCl) structure Zinc blende/sulfide (ZnS) structure
AmXp-type crystal structures Charges on cations and anions are different (m p 1) Calcium fluoride (CaF2) structure Zirconium dioxide (ZrO2) structure AmBnXp-type crystal structures More than one type of cation (represented by A and B) Barium titanite (BaTiO3) structure

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Types of Crystal Structures Summary of some common ceramic crystal structures

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Sodium Chloride Crystal Structure


FCC arrangement of anions Highly Ionically bonded with Na+ ions occupying interstitial sites between FCC and Cl- ions. One cation at the cube center and one at the center of each of the 12 cube edges Radius ratio = 0.56, CN = 6. MgO, CaO, NiO and FeO have similar structures.

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MgO and FeO

MgO and FeO also have the NaCl structure


O2Mg2+ rO = 0.140 nm rMg = 0.072 nm

rMg/rO = 0.514
cations prefer OH sites

So each oxygen has 6 neighboring Mg2+


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AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende Cesium Chloride structure:

rCs rCl

0.170 0.939 0.181

cubic sites preferred So each Cs+ has 8 neighboring Cl-

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Cesium Chloride (CsCl) Structure


Anions located at each of the cube corners One cation at the cube center This is not a BCC crystal structure since ions of two different kinds involved

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Zinc Blende (ZnS) Crystal Structue Four zinc and four sulfur atoms. Zn2 0.074 0.529 OH ?? rO2 0.140 FCC arrangement of S atom S occupies lattice points and Zn occupies interstitial sites of FCC unit cell. S Atoms (0,0,0) ( , ,0) ( , 0, ) (0, , ) Zn Atoms ( , , ) ( , , )( ,, ) ( , , ) Atomic bonding is highly covalent. (87% covalent character) with CN = 8. CdS, InAs, InSb and ZnSe have similar structures.
r

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Mechanical Properties

We know that ceramics are more brittle than metals. Why? Consider method of deformation
slippage along slip planes
in ionic solids this slippage is very difficult too much energy needed to move one anion past another anion

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Ceramic Density Computations


Theoretical density of a crystalline ceramic material can be determined as follow

mass of unit cell = mass of total equivalent number of anions and cations

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Example
Question 1: Compute the theoretical density of sodium chloride (NaCl) on the basis of crystal structure. Atomic weights of Na and Cl are 22.99 g/mol and 35.45 g/mol respectively. The ionic radii of Na+ and Clare 0.102 and 0.181 nm respectively.

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Question 2
Compute the theoretical density of zinc blende (ZnS) on the basis of crystal structure. Atomic weights of Zn and S are 65.37 g/mol and 32.06 g/mol respectively. The ionic radii of Zn2+ and S2- are 0.06 and 0.174 nm respectively.

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Silicate Ceramics
Most common elements on earth are Si & O

Si4+

O2-

crystobalite

SiO2 (silica) structures are quartz, crystobalite, & tridymite The strong Si-O bond leads to a strong, high melting material (1710 C)

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Silicate Ceramics

The structures of silicate ceramics are generally complex: the atoms are not closely-packed together Relatively low density due to nonclosely-packed atoms
For the various silicate minerals, one, two or three of the corner oxygen atoms of Si044- tetrahedra are shared by other tetrahedra to form complex structures (often noncrystalline)

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Silica Glass

Dense form of amorphous silica


Charge imbalance corrected with counter cations such as Na+ Borosilicate glass is the pyrex glass used in labs
better temperature stability & less brittle than sodium glass

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Silicates
Combine SiO44- tetrahedra by having them share corners, edges, or faces

Cations such as Ca2+, Mg2+, & Al3+ act to neutralize & provide ionic bonding
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Carbon and Its Allotropes

Carbon has many allotropes, i.e. exist in many crystalline forms These allotropes have different crystal structures and properties
Diamond Graphite Fullerenes Carbon nanotubes Carbon does not really fall within ceramic classification. Only graphite is often considered as ceramic materials

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Carbon and Its Allotropes

Diamond Each carbon bonds to four other carbon (totally covalent). Its crysta structure is similar with Zinc Blende (ZnS)

Stiffest, hardest and least compressible material due to strong coval bonding Optically transparent, excellent electrical insulator and thermal conductor Industrially, used to increase surface hardness, e.g. drills bits and cutting tools

Carbon Forms - Graphite


Composed of layers of hexagonally arranged carbon atoms layer structure aromatic layers weak van der Waals forces between layers and strong covalent bonding within layers planes slide easily, good lubricant Industrially, used as electrdes for arc welding, pencils casting, molds, high-temperature refractories

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Carbon Forms - Fullerenes


Fullerenes Exists in discrete molecular form Consists of a hollow spherical cluster of sixty carbon atoms Single molecule is denoted by C60 and consists of 20 hexagons and 12 pentagons arrangement such that no two pentagons share a common side Has FCC structure with one C60 at each FCC lattice point Used in fuel cells, lubricants and semiconductors

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Carbon Forms Carbon Nanotubes


Carbon nanotubes Consists of a single sheet of graphite, rolled into a tube where both ends are capped with C60 hemispheres Tube diameters are on the order of nanometer, i.e. 100 nm or less Extremely strong and stiff; relatively ductile Tensile strength of 50-200 GPa; modulus of elasticity on the order of 1 TPa (Tetra-Pascal: 1TPa = 1000 GPa); fracture strains 5-20%

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Defects in Ceramic Structures


Frenkel Defect --a cation is out of place. Shottky Defect --a paired set of cation and anion vacancies. Shottky Defect:

Frenkel Defect Equilibrium concentration of defects ~e D The equilibrium number of atomic defects increases with temperature
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Q / kT

Defects in Ceramic Structures


Defects in ceramics do not occur alone in order to maintain electro-neutrality Frenkel defect: Cation leaving its normal position and moving into an interstitial site Schottky defect: Removing one cation and one anion from the crystal

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Impurities
Impurities must also satisfy charge balance = Electroneutrality Cl Ex: NaCl Na +

Substitutional cation impurity Ca2+ Na+ Na+ initial geometry Ca2+ impurity Substitutional anion impurity O2Cl- Clinitial geometry O2- impurity

cation vacancy

Ca2+ resulting geometry anion vacancy

resulting geometry

Defects in Ceramics
The equilibrium number of Frenkel and Schottky defects increases with temperature according to

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Mechanical Properties of Ceramics General properties Relatively brittle, fracture occurs before any plastic deformation Large difference between tensile and compressive strength (10 times higher in compression) Strength depends significantly on the presence of flaws and porosity (void, decreases cross sectional area)

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Mechanical Properties of Ceramics


Stress-strain behavior Stress-strain behavior is not usually ascertained by a tensile test: Difficulty in gripping brittle materials without fracturing them, ceramics fail after only 0.1% of strain employed: three- or four-point bending test Specimen is bent until fracture. Top surface under compression, bottom surface under tension

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Measuring Strength
3-point bend test to measure room T strength.
cross section

L/2

L/2
d = midpoint deflection

d
rect.

R
circ.
location of max tension

Flexural strength:
s

fs

1.5Ff L bd 2

(Rectangular cross sectional area)

Ff L

pR3

(Circular Cross sectional area)

Flexural strength Defined by the stress at fracture during the bending test Computed using the following equations

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Measuring Elastic Modulus


Room T behavior is usually elastic, with brittle failure. 3-Point Bend Testing often used. --tensile tests are difficult for brittle materials. F cross section L/2 L/2 d R b d = midpoint rect. circ. deflection Determine elastic modulus according to: F F L3 F L3 = E= x d 4 bd 3 d 12 p R 4 F slope = rect. circ. d cross cross d section section linear-elastic behavior
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Mechanical Properties of Ceramics

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Mechanical Properties of Ceramics Influence of porosity Porosity is a measure of void spaces in materials In ceramics, porosity is introduced during the fabrication Porosity decreases significantly the strength of materials

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Example
Question The flexural strength and associated volume fraction porosity for two specimens of the same ceramic material are given in the table below. (a) Compute the flexural strength for a completely non-porous specimen

(b) Compute the flexural strength for a 0.20 volume fraction porosity

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