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Chapter 13 Structures and Properties of Ceramics
Chapter 13 Structures and Properties of Ceramics
Chapter 13: Structure and Properties of Ceramics Crystal Structures Silicate Ceramics Carbon Imperfections in Ceramics Optional reading: 13.6 13.10
Chapter 14: Applications and Processing of Ceramics Short review of glass/ceramics applications and processing (14.1 - 14.7) Optional reading: 14.8 14.18
Ceramics
keramikos - burnt stuff in Greek - desirable properties of ceramics are normally achieved through a hightemperature heat treatment process (firing). Usually a compound between metallic and nonmetallic elements Always composed of more than one element (e.g., Al2O3, NaCl, SiC, SiO2) Bonds are partially or totally ionic, and can have combination of ionic and covalent bonding Generally hard and brittle Generally electrical and thermal insulators Can be optically transparent opaque, semi-transparent, or
Traditional ceramics based on clay (china, bricks, tiles, porcelain), glasses. New ceramics for electronic, computer, aerospace industries.
University of Tennessee, Dept. of Materials Science and Engineering 2
Electronegativity - a measure of how willing atoms are to accept electrons (subshells with one electron - low electronegativity; subshells with one missing electron high electronegativity). Electronegativity increases from left to right. The atomic bonding in ceramics is mixed, ionic and covalent, the degree of ionic character depends on the difference of electronegativity between the cations (+) and anions (-).
University of Tennessee, Dept. of Materials Science and Engineering 3
Coordination Number
The number of adjacent atoms (ions) surrounding a reference atom (ion) without overlap of electron orbitals. Also called ligancy Depends on ion size (close packed) Ideal: Like-sized atoms = 12 Calculated by considering the greatest number of larger ions (radius R) that can be in contact with the smaller one (radius r).
R=1.0 r =0.2
CN = 1 possible
CN = 2 possible
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Coordination Number
CN numbers for ionic bonding CN r/R 2 0<r/R<0.155 3 0.155r/R<0.225 4 0.225r/R<0.414 6 0.414r/R<0.732 8 0.732r/R<1 12 1
Example: KCl K+ r=0.133nm, Cl- R=0.188nm, r/R = 0.71, CN = 6 Example: CsCl Cs+ r=0.165nm, Cl- R=0.188nm, r/R = 0.91, CN = 8 Example: Al2O3 Al+3 r=0.057nm, O-2 R=0.132 nm, r/R = 0.43, CN = 6 However for O-2 CN= (2/3) (6) =4 [(2/3) = (cation/ion) ratio]
University of Tennessee, Dept. of Materials Science and Engineering 6
C.N.
rC/rA
Geometry
<0.155
0.155-0225
0.225-0.414
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0.414-0.732
Two interpenetrating FCC lattices NaCl, MgO, LiF, FeO have this crystal structure
University of Tennessee, Dept. of Materials Science and Engineering 9
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Semiconductor Structures
Structure: diamond cubic Bravais lattice: fcc Ions/unit cell: 4 + 6 x + 8 x = 8 Typical ceramics: Si, Ge, and gray Sn
University of Tennessee, Dept. of Materials Science and Engineering 11
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Crystal structure depends upon: (1) stacking sequence (hcp or fcc) and (ii) interstitial sites occupied by cations E.g. NaCl: Cl anions packed in fcc symmetry (ABCABC), Na cations on octahedral sites Spinel (MgAl2O4): O anions form fcc lattice, Mg cations in tetrahedral sites, Al cations in octahedral sites
How to Differentiate?
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AC: sum of atomic weights of cations in the formula unit AA: sum of atomic weights of anions in the formula unit Vc : NA: volume of the unit cell Avogadros units)/mol number, 6.0231023 (formula
Example: NaCl n = 4 in FCC lattice AC = ANa = 22.99 g/mol AA = ACl = 35.45 g/mol Vc = a3 = (2rNa+2rCl)3 = = (20.10210-7 + 20.18110-7)3 cm3
University of Tennessee, Dept. of Materials Science and Engineering 15
Silicate Ceramics
Composed mainly of silicon and oxygen, the two most abundant elements in earths crust (rocks, soils, clays, sand) Basic building block: SiO44- tetrahedron Si-O bonding is largely covalent, but overall SiO4 block has charge of 4 Various silicate structures different ways to arrange SiO4-4 blocks
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Window glasses
Most common window glasses are produced by adding other oxides (e.g. CaO, Na2O) whose cations are incorporated within SiO4 network. The cations break the tetrahedral network and glasses melt at lower temperature than pure amorphous SiO2 because. A lower melting point makes it easy to form glass to make, for instance, bottles. Some other oxides (TiO2, Al2O3 substitute for silicon and become part of the network
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Carbon
Carbon is not a ceramic Carbon exists in various polymorphic forms: sp3 diamond graphite and and amorphous carbon, sp2 fullerenes/nanotubes, one dimensional sp carbon
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Carbon: Diamond
Has diamond-cubic structure (like Si, Ge) One of the strongest/hardest material known High thermal conductivity (unlike ceramics) Transparent in the visible and infrared, with high index of refraction, looks nice, costs $$$ Semiconductor (can be doped to make electronic devices) Metastable (transforms to carbon when heated)
of Tennessee, Dept. of Materials Science and Engineering Figures University from http://www.people.virginia.edu/~lz2n/Diamond.html 20
~ 100 microns
Chemical vapor deposition (CVD) Thin films up to a few hundred microns Polycrystalline Applications: hard coatings (tool bits etc), machine components, heat sinks for high power semiconductor devices
University of Tennessee, Dept. of Materials Science and Engineering 21
Carbon: Graphite
Layered structure with strong bonding within the planar layers and weak, van der Waals bonding between layers Easy interplanar cleavage, applications as a lubricant and for writing (pencils) Good electrical conductor Chemically stable even at high temperatures Applications include furnaces, rocket nozzles, welding electrodes
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Nano-gear
Nanotube holepunching/etching
University Tennessee, Dept. of Materials Science and Engineering Figures from of http://www.nas.nasa.gov/Groups/SciTech/nano/ 23
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Impurities in Ceramics
Impurity atoms can exist as either substitutional or interstitial solid solutions Substitutional ions substitute for ions of like type Interstitial ions are small compared to host structure anion interstitials unlikely Solubilities higher if ion radii and charges match closely Incorporation of ion with different charge state requires compensation by point defects
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Stress (MPa)
(a) Tension ()
Stress (MPa)
(b) Compression ()
The brittle nature if fracture is illustrated by these stress-strain curves, which show only linear, elastic behavior.
The bending test that generates a modulus of rupture, this strength is similar to the tensile strength.
University of Tennessee, Dept. of Materials Science and Engineering 29
Plastic Deformation in Ceramics Crystalline ceramics: Slip (dislocation motion) is very difficult. This is because ions of like charge has to be brought into close proximity of each other large barrier for dislocation motion. In ceramics with covalent bonding slip is not easy as well (covalent bonds are strong). ceramics are brittle. Non-crystalline ceramic: there is no regular crystalline structure no dislocations. Materials deform by viscous flow, i.e. by breaking and reforming of atomic bonds, allowing ions/atoms to slide past each other (like in a liquid). Viscosity is a measure of glassy materials resistance to deformation.
FA = dv dy dv dy
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Summary
Make sure you understand language and concepts: Anion Cation Defect structure Frenkel defect Electroneutrality Schottky defect Stoichiometry Viscosity
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Chapter 14: Applications and Processing of Ceramics Short review of glass/ceramics applications and processing (14.1 - 14.7) Optional reading: 14.8 14.18
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