Lec 10: Ceramic Materials I

Sunday, 27 March 2016 6:22 PM

IMPORTANT PROPERTIES, SOURCES & STRUCTURE

3.6 CERAMIC CRYSTAL STRUCTURES

Composed of at least TWO elements
Their crystal structures are generally more complex than those for metals
Atomic bonding: purely IONIC to totally COVALENT
Many ceramics exhibit a combination of these two bonding types
The degree of ionic character being dependent on the electronegativities of the atoms
IONIC
The crystal structures may be thought of as being composed of electrically charged ions instead of atoms
Cations
Metallic ions that are positively charged because they have given up their valence electrons to the
nonmetallic ions
Anions
Nonmetallic ions which are negatively charged
2 characteristics (of the component ions in crystalline ceraimc materials influence the crystal structure
1. Magnitude of the electrical charge on each of the component ions
The crystal must be electrically NEUTRAL
All the cation positive charges must be balanced by an equal number of anion negative charges.
The chemical formula of a compound indicates the ration of cations to anions, or the composition that
achieves this charge balance.
Example: Calcium flouride, each calcium ion has a +2 charge (Ca2+); Fluorine ion is a single
negative charge (F-)
There must be twice as many F- as Ca2+ ions, CaF2
2. Relative size or ionic radii of the cations, rc and anions, rA
Metallic elements give up electrons when ionized, cations are ordinarily smaller than anions
Ratio rC/rA < 1
Each cation prefers to have as many nearest-neighbor anions as possible.
The anions also desire a maximum number of cation nearest neighbors.
Stable ceramic crystal structures form when those anions surrounding a cation are all in contact with that cation.

Coordination number - number of anion nearest neighbors for a cation

The CN is related to the cation-anion radius ratio
For a specific CN, there is a critical or minimum rC/rA ratio for which this cation-anion contact is
established, which ration may be determined from pure geometrical considerations.

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 Very small cation is bonded
to two anions in a linear
manner

CN: 3, each cation is surrounded by 3 anions in

the form of a planar equilateral triangle, with the
cation located in the center

CN: 4; cation is located at the center of a

tetrahedron, with anions at each of the four corners

Cation may be thought of as being situated at the center

of an octahedron surrounded by six anions, one at each
corner

CN: 8; anions at all corners of a cube and a cation

positioned at the center

CN: 12; for radius greater than unity

Most common CN: 4, 6 and 8

AX-Type Crystal Structures

Equal numbers of cations and anions

A - cation; X - anion
Named after a common material that assumes the particular structure

1. Rock Salt Structure

NaCl or rock salt type

CN for both cations and anions: 6
Cation-anion radius = ~ between 0.414-0.732
Unit cell

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 Unit cell
An FCC arrangement of anions with one cation situated at the cube center and one at the center of
each of the 12 cube edges
An equivalent crystal structure results from a face-centered arrangement of cations
May be thought of as two interpenetrating FCC lattices, one composed of the cations, the other of
anions
Examples: NaCl, MgO, MnS, LiF, FeO

2. Cesium Chloride Structure

CN: 8 for both ion types

Anions are located at each of the corners of a cube; cube center is a single cation
Interchange of anions with cations, and vice versa, produces the same crystal structure
This is NOT A BCC crystal structure because ions of two different kinds are involved
3. Zinc Blende Structure

Zinc blende or sphalerite (i.e. mineralogical term for ZnS)

CN: 4
All ions are tetrahedrally coordinated
Unit cell: corner and face positions of the cubic cell are occupied by S atoms; Zn atoms fill interior tetrahedral
positions
An equivalent structure results if Zn and S atom positions are reversed.
Thus, each Zn atom is bonded to four S atoms, and vice versa
Atomic bonding is highly covalent
Examples: ZnS, ZnTe, SiC

AmXp-type Crystal Structure

Charges on the cations and anions are not the same
Chemical formula: AmXp, where m and/or p 1

1. AX2

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Common crystal structure is found in fluorite (CaF2)

Ionic radii ratio rC/rA: 0.8; CN: 8
Ca ions are positioned at the centers of cubes, with Fl ions at the corners
Chemical formula: only half as many Ca2+ ions as F- ions, crystal structure would be similar to CsCl, except
that only half the center cube positions are occupied by Ca2+ ions
One unit cell consists of 8 cubes
Examples: UO2, PuO2 and ThO2

AmBnXp-type Crystal Structure

More than one type of cation

2 types of cation: represented by A and B
Chemical formula: AmBnXp

1. Perovskite crystal structure

Example: Barium titanate (BaTiO3)

Ba2+ and Ti4+ cations
Above 120 C - cubic
Ba2+ ions - situated at all 8 corners of the cube and a single Ti4+ is at the cube center, with O2- ions located
at the center of each of the six faces

12.3 SILICATE CERAMICS

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Introduction
Silicates - materials composed primarily of silicon and oxygen
2 most abundant elements in the earth's crust
Bulk of soils, rocks, clays, and sand come under the silicate classification
Crystal structure: more convenient to use various arrangements of an tetrahedron

Silicate basic unit

Each atom of silicon is bonded to four oxygen atoms, which are situated at the corners of the tetrahedron; the
silicon atom is positioned at the center.
Negatively charged entity
Ionic vs. covalent
Often the silicates are not considered to be ionic because there is a significant covalent character to the
interatomic Si-O bonds, which are directional and relatively strong.
-4 charge
Associated with every tetrahedron aince each of the 4 oxygen atoms requires an extra electron to
achieve a stable electronic structure
Regardless of the character of the Si-O bond
Various silicate structures arise from the different ways in which the units can be combined into one-, two-,
and three-dimensional arrangements.

SILICA
Silicon dioxide or silica (SiO2)
Structure
A three-dimensional network
Every corner oxygen atom in each tetrahedron is shared by adjacent tetrahedra
Thus, material is electrically neutral and all atoms have stable electronic structures
Si:O - 1:2
If these tetrahedra are arrayed in a regular and ordered manner, a crystalline structure is formed.
3 primary polymorphic crystalline forms of silica:
Quartz
Cristobalite

Tridymite
Atoms are not closely-packed together.
Relatively low densities
Density of quartz @ room temp - 2.65 g/cm3
Strength of Si-O interatomic bonds
Reflected in a relatively high melting temperature - 1710 C

SILICA GLASSES
Fused silica or vitreous
Silica can also be made to exist as a noncrystalline solid or glass, having a high degree of atomic randomness,
which is characteristic of the liquid

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Network formers
Other oxides that form glassy structures and polyhedral oxide structures
B2O3, GeO2, SiO2
Silica glasses - commom inorganic glasses that are used for containers, windows and so on to which have been
added other oxides such as CaO and Na2O
These oxides do not form polyhedral networks, rather, their cations are incorporated within and modify the
network; for this reason, these oxide additives are termed network modifiers.

Intermediates
Other oxides that, while not network formers, substitute for silicon and become part of and stabilize the
network
TiO2 and Al2O3
Modifiers and intermediates lowers the melting point and viscosity of a glass, and makes it easier to form at lower
temperatures.

THE SILICATES

Introduction
For the various silicate minerals, one, two or three of the corner oxygen atoms of the terahedra are shared by
other tetrahedra to form some rather complex structures.

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 other tetrahedra to form some rather complex structures.

(e) single-chain structures

Positively charged cations
Ca2+, Mg2+, Al3+
2 roles
1. Charge neutrality
Compensate the negative charges from the units so that charge neutrality is
achieved
2. Ionic bonding
Ionically bond the tetrahedra together
Simple Silicates
Isolated tetrahedra
Fig. 3.12a
Forsterite (Mg2SiO4)
2 Mg2+ ions associated with each tetrahedron in such a way that every Mg2+ ion has six oxygen nearest
neighbors
ion
2 tetrahedra share a common oxygen atom
Akermanite (Ca2MgSi2O7)
2 Ca2+ ions and one Mg2+ ion bonded to each unit

Layered Silicates
A two-dimensional sheet or layered structure can also be produced by the sharing of three oxygen ions in each of the
tetrahedra

Repeating unit formula

Fig. 3.13 - single sheet

Net negative charge

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 Net negative charge
Associated with the unbonded oxygen atoms projecting out of the plane of the page
Electroneutrality
Ordinarily established by a second plane sheet structure having an excess of cations, which bond to these
unbonded oxygen atoms from the Si2O5 sheet - SHEET OR LAYERED SILICATES
Basic structure is characteristic of the clays and other minerals
1. Kaolinite
Clay mineral
Structure: two-layer silicate sheet structure
Formula: Al2(Si2O5)(OH)4
Silica tetrahedral layer, is made electrically neutral by an adjacent Al2(OH)42+ layer

Midplane of anions
Consists of O2- ions from the layer and OH- ions that are part of the Al2(OH)42+
layer
Bonding within this two-layered sheet
Strong and intermediate ionic-covalent
Adjacent sheets
Loosely bound to one another by weak van der Waals force
Crystal is made of a series of these double layers or sheets stacked parallel to each other, which form
small flat plates typically less than 1 micron in diameter and nearly hexagonal
Electron micrograph of kaolinite crystals
Shows hexagonal crystal plates some of which are piled one on top of the other
p.383 of book
2. Talc
Mg3(Si2O5)2(OH)2
Mineral
Important ceramic raw material
3. Micas
Mineral
e.g. Muscovite, KAl3Si3O10(OH)2
Important ceramic raw material

12.4 CARBON

Introduction
An element that exists in vaarious polymorphic forms, as well as in the amorphouos state.
This group of materials does not really fall within any one of the traditional metal, ceramic, polymer classification
schemes.
Discussed in this chapter since graphite, one of the polymorphic forms is sometimes classifies as a ceramic
In additon, the crystal structure of diamond, another polymorph, is similar to that of zinc blende
Polymorph - any of the crystalline forms of a polymorphic substance

DIAMOND
A metastable carbon polymorph at room temperature and atmospheric pressure.
DIAMOND CUBIC Crystal structure: variant of the zinc blende, in which C atoms occupy all positions

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Each bonds to 4 other carbons, and these bonds are totally covalent
Also found for other Group IV1 elements in the periodic table: germanium, silicon and gray tin, below 13 C
Physical properties:
Extremely hard; hardest known material
Very low electrical conductivity
Due to its crystal structure and strong interatomic covalent bonds
High thermal conductivity
For a nonmetallic material
Optically transparent in the visible and infrared regions of the electromagnetic spectrum
High index of refraction
Uses: gems and for grinding and cutting other softer materials
Diamond thin films
Film growth techniques: vapor-phase chemical reactions followed by fim deposition
Max film thickness: mm
Diamond is polycrystalline and may consist of very small and/or relatively large grains; in addition
amorphous carbon and graphite may be present
Mechanical, electrical, and optical properties approach those of the bulkl diamond material
Application: diamond film coatings
Surfaces of drills, dies, bearings, knives and other tools have been coated with diamond films to increase
surface hardness
Lenses and radomes have been made stronger while remaining transparent
Loudspeaker tweeters and to high-precision micrometers
Surface of machine components such as gears, to optical recording heads and disks
Substrates for semiconductor devices

GRAPHITE
Distinctly different from that of diamond
More stable than diamond at ambient temperature and pressure
Structure

Composed of layers of hexagonally arranged C atoms; within the layers, each C atom is bonded to three
coplanar neighbor atoms by strong covalent bonds
Fourth bonding electron participates in a weak van der Waals type of bond between the layers
Hence, interplanar cleavage is facile, which gives rise to the excellent lubricative properties of graphite
Properties
Relatively high electrical conductivity
High in crystallographic directions parallel to the hexagonal sheets
High strength and good chemical stability

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 High strength and good chemical stability
at elevated temperatures and nonoxidizing atmospheres
High thermal conductivity
Low CTE and high resistance to thermal shock
High adsorption of gases
Good machinability
Application
Heating elements for electric furnaces
Electrodes for arc welding
Metallurgical crucibles
Casting molds for metal alloys and ceramics
For high temperature refractories and insulations
In rocket nozzles
In chemical reactor vessels
For elctrical contacts, brushess and resistors
As electrodes in batteries
In air purification devices

FULLERENES
Discovered in 1985
Exists in discrete molecular form
Structure

Consists of a hollow spherical cluster of 60 carbon atoms

A single molecule is designated by C60
Molecule
Composed of groups of C atoms that are bonded to one another to form both hexagon (6-C atom) and
pentagon (5-C atom) geometrical configurations
Consists of 20 hexagons and 12 pentagons
Arrayed such that no two pentagons share a common side
The molecular surface thus exhibits the symmetry of a soccer ball
Buckminsterfullerene
Material composed of C60 molecules
Named in honor of R. Buckminster Fuller who inveneted the geodesic dome
Each C60 is simply a molecular replic of such a dome, which is often referred to as a "buckyball" for
short
Fullerene - denote the class of materials that are composed of this type of molecule
Network solids
Diamond and graphite
All of the C atoms form primary bonds with djacent atoms throughout the enturety of the solid
The C atoms in buckministerfullerene bond together so as to form these spherical molecules.
In the solid state, C60 units form a crystalline structure and pack together in a FCC array.
Properties
As a pure crystalline solid, this material is electrically insulating.
With proper impurity additions - highly conductive and semi-conductive

CARBON NANOTUBES
Structure
Consists of a single sheet of graphite, rolled into a tube, both ends of which are capped with C60 fullerene
hemispheres
Nano
Tube diameters are on the order of a nm (i.e. 100 nm or less)

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 Tube diameters are on the order of a nm (i.e. 100 nm or less)
Nanotube
Each nanotube is a singlel molecule composued of millions of atoms
Length - much greater than its diameter (thousand of times greaterr)
Multiple-walled carbon nanotubes exist consisting of concentric cylinders.
Termed as the "ultimate fiber"
Properties
1. String and stiff
2. Relatively ductile
3. Tensile strengths
For single-walled nanotubes, between 50 and 200 Gpa
Strongest known material
4. Elastic modulus
One tetrapascal, 1 TPa = 103 Gpa
5. Fracture strains
Between 5% and 20%
6. Relatively low densities
7. Unique and structure-sensitive electrical characteristics
Depending on the orientation of the hexagonal units in the graphene plane (i.e. Tube wall) with the tube
axis, nanotube may behave electrically a metal or a semiconductor
Application
Field emitters of flat-panel and full-color displays
Cheaper and have lower power requirements than CRT and LCD
Diodes and transistors

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