CERAMICS & GLASS

REFF: Materials Science & Engineering; An Introduction Callister, W. D, Jr, 2007, John Wiley & Sons Fundamental of Ceramics, Barsoum, M. W., 2003, McGraw-Hill Engineering Materials 2; An Introduction to Microstructures, Processing and Design, Ashby, M. F and Jones, D. R. H, 1986, Pergamon Press

Introduction
CERAMICS: Greek keramikos = burn stuff solid compounds formed by heat (&/P) applications followed by cooling at least 2 elements; 1 is a non-metal, the other may be (a) metal(s) or (an)other non Oxygen and silicon are abundance in nature: rocks, dust, clay, mud

Atom arrangement

In ceramics: long-range order, short-range order or both combination Long-range order: repeat periodicity >>bond length cryatalline solid;ceramics Short-range order:No periodicity amorphous, glassy or noncrystalline solid; glass

1 unit cell: the smallest region when repeated, completely describes 3D atoms of crystal Crystalline solid: single crytals & polycrystalline solids Single crystal: solid in which the periodic & repeated arrangement of atom is perfect & extends specimen entire, no interruption

Polycrystalline solid: many single crystals (grains), separated each other by disorder area (grain boundaries)

General Characteristics of Ceramics

Hard Wear-resistant Brittle Prone to thermal shock Resistant to usual treatment Oxidation resistant Chemically stable

Nonmagnetic Electrically & thermally insulative

Ionic Vs Covalent Bonding

Ionic compound form between very active metallic & nonmetallic elements To form AX ionic bonding, A loses e easily, X accepts e without too much energy input Covalent bonding occurs if energies of bonding electrons of A & X are comparable If the electron energy of the atoms is different transfer energy (ionic bonding)

Ceramic Structures
Atomic bonding: purely ionic to totally covalent, many exhibit combination type Degree of ionic character electronegativities of atoms Electronegativity (e greed): the power of atom to attract electrons to itself Two elements forming a bond have similar electronegativity share e; covalent bond

Mutual attraction lower potential energy If the electronegativity difference between them (x)is large (indicating 1 element is greedier than other), e attracted to the more electronegative element ion attract each other x > 1.7 ionic x < 1.7 covalent

Character of ionic compounds: have high melting & boiling points (the bonds are strong and omnidirectonal), hard, brittle, poor electrical and thermal conductors

Crystal Structure
Ionic bonding composed of electrically charge ions instead of atoms Metalic ions (cation, + charge) give valence electron to the nonmetalic Characteristics of ions which affect crystal structure: 1. magnitude of electrical charged of each ions 2. relative size of + and - ion

Crystal electrically neutral; (+) charges must be balanced by an equal number of () related to the chemical formula Each cation prefers as many neighbour anions, anions also desire a maximum number of cation. Coordination no. (number of anions neighbors for a cation) related to rc/ra Stable structures require that cations and anions touch

Table: Coordination numbers and geometries for various rc/ra Blue cation Red anion Common coordination numbers for ceramic: 4, 6 and 8

The size of an ion depend on: 1. coordination number Ionic radius increase as the number of opposite charge neighbor ions increases 2. number of e of atom/ion Removing e from atom/ion, the remaining valence electrons become more tightly bound to the nucleus decrease ionic radius. Ionic size increases when electrons are added to an atom or ion.

AX-type crystal structures

Ceramic of metal & nonmetal element (AX) with equal number of A (cation) & X (anion) Ionic MgO; 2 e of A transferred to X, result in Mg2+ & O2 Covalent ZnS; sharing elektron 3 structures: rock salt, CeCl and ZnS

Rock salt (NaCl) structure

The most common AX crystal structure Electrostatic attraction between Na+ & Cl- hold the crystal together Max. electrostatic interaction each Na+ has 6 Cl-, no Na+ neighbours (vice versa) Coordination number for both + & - is 6 (octahedral) 1 unit cell generated from FCC of anion with 1 cation in cubic center & 1 at centered of each of 12 cube edge NaCl, MgO, MnS, LiF and FeO

Cesium cloride (CsCl) stucture

Coordination number for both ions is 8 (cubic) The anions are at each of the corners of a cube Single cation is at the cube center

Zinc Blende (ZnS) structure

Coordinate number for both ions is 4 (tetrahedral) all corner and face positions of the cubic cell are occupied by S atoms the Zn atoms fill interior tetrahedral positions Most often the atomic bonding is highly covalent ZnS, ZnTe, and SiC

SILICATE CERAMIC

Material composed primarily of silicon and oxygen Each silicon atom bond strongly to 4 oxygen atom Basic unit in all silicates tetrahedron (oxygen are situated at the corners, oxygen is at the centre)

The most simple: silicon dioxide/silica Pure silica no metal ions, every oxygen becomes a bridge between 2 silicon atoms Every corner oxygen atom is shared by adjacent tetrahedra The materials electrically neutral, all atoms have stable electronic structures Ratio Si to O 1:2 (indicated by chemical formula) If tetrahedras are arranged in a regular & order crystalline 3 polymorphic: quartz, cristobalite & tridymite

Tetrahedra link: directly or via metal ion (M) Silicas combined with metal oxides (e.g. MgO, CaO, Al2O3) MO/SiO2 2 separated SiO4 monomer linked by MO molecules MO/SiO2 < 2 silica dimers;1oxygens shared between 2 tetrahedra (bridging oxygen)

Decrease amount of MO increase degree of polymerisation Chain form linked tetrahedra Backbone Si-O-Si-O-Si-; 2 oxygens of each tetrahedron are shared (2 bridging oxygens) The others forms ionic bonds between chains, joined by MO; weaker than backbonefibrous E.g. asbeston

Sheet form 3 oxygen of each tetrahedron are shared; e.g. clay M attached to one of side of sheet (side with spare oxygen on it) The sheet is polarised a net + charge on one surface, - charge on the other This interaction strongly with water, attract a water layer between the sheets clay plastic

Silica Glasses

Commercial glasses are based on silica Silica also exist as noncrystalline solid/glass fused silica/vitreous silica Pure silica forms glass with high softening T (1200 C) Great strength and stability, low thermal expansion but hard to work with because high in viscosity

Commercial glasses silica glasses add with other metal oxide to reduce viscosity E.g. CaO, Na2O add positive ion to the structure &break up the network network modifiers Add 1 Na2O molecules introduces 2 Na+, each attaches to 1 oxygen of tetrahedron non bridging

TiO2, Al2O3 substitute silicon; become part and stabilize the network intermediates Reduction in cross-linking/ substitute silicon soften the glass, reduce Tm, viscosity of glass easier to form at low T Common window glass: 70% SiO2, easily work at 700 C Pyrex: 80% SiO2, less modifier, better thermal shock resistance, thermal expansions lower, harder work (800 C)