Beruflich Dokumente
Kultur Dokumente
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?
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
Introduction
Common objects made of ceramic materials
Building brick
Cup
Glass vase
Scissors
Floor tile
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)
Ceramic Bonding
Bonding: -- Mostly ionic, some covalent. -- % ionic character increases with difference in electronegativity. Large vs small ionic bond character: CaF2: large
SiC: small
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%
Example
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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unstable
stable
stable
If the anion does not touch the cation, then the arrangement is unstable.
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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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--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 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+
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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rMg/rO = 0.514
cations prefer OH sites
AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende Cesium Chloride structure:
rCs rCl
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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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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
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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
32 Prepared by Dr. Ang Bee Chin
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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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
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Frenkel Defect Equilibrium concentration of defects ~e D The equilibrium number of atomic defects increases with temperature
38 Prepared by Dr. Ang Bee Chin
Q / kT
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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
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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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
Ff L
pR3
Flexural strength Defined by the stress at fracture during the bending test Computed using the following equations
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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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