Chapter 3 STRUCTURES OF METALS AND CERAMICS

The Next Level Into the Crystals

Discussed about atoms and how they bond Moving into the arrangements of atoms and how they form a structure Crystallinity and Non-Crystallinity

Crystalline Materials

Crystal: A solid with atoms arranged in a repeating or periodic array over large atomic distances Long range order exists Repetitive 3-D pattern Each atom is bonded to its nearest-neighbor atoms Simple arrangement for metals, extremely complex for polymers and ceramics Properties depend on the spatial atomic arrangement

Li3N

Atomic Packing and Crystallinity

Local arrangement of atoms in a solid is usually predictable This may be in long range repeating structure Crystalline This may be in short irregular sections Amorphous or Glassy Arrangement depends on bond

Materials and Packing

atoms pack in periodic, 3D arrays typical of: -metals -many ceramics -some polymers

Crystalline materials

crystalline SiO2
Adapted from Fig. 3.41(a), Callister & Rethwisch 4e.

Non-Crystalline materials

Si

Oxygen

atoms have no periodic packing occurs for: -complex structures -rapid cooling "Amorphous" = Noncrystalline
noncrystalline SiO2
Adapted from Fig. 3.41(b), Callister & Rethwisch 4e. 5

Terminology

Atomic Hard Sphere Model: Atoms are thought of as hard spheres with well defined diameters

Spheres representing the nearest neighbor atoms touch one another

Stable materials want to stack together nicely

Lattice and Unit Cell

Lattice: 3-D array of points coinciding with the atom positions (sphere centers) Unit Cell: The smallest repeating entities in a crystal structure

Crystal Systems

A vast array of possible crystal structures Convenient to divide them into groups based on cell configurations or atomic arrangements Most common based on Unit Cell Geometry Defining the unit cell geometry in terms of six parameters 3 edge lengths and 3 interaxial angles Crystals having seven possible combinations of edge lengths and interaxial angles

Metallic Crystal Structures

Metallic bonding Non-directional Typically, all atomic radii are the same Large number of nearest neighbor atoms, leading to a high packing density Three crystal structures observed in general:

Face-Centered Cubic (FCC) Body-Centered Cubic (BCC) Hexagonal Close Packed (HCP)

3 Cubic Crystal Types

Simple Cubic

Body-Centered Cubic (BCC) Reduced Sphere Models

Face-Centered Cubic (FCC)

More Terminology

Co-Ordination Number: The number of nearest neighbor, or touching atoms Atomic Packing Factor (APF): Fraction of solid sphere volume in a unit cell (assuming the atomic hard sphere model)
APF Volume of atoms in unit cell Total volume of the unit cell

Simple Cubic Structure

Rare Poor packing

APF = 0.52

Co-ordination number - 6

Body-Centered Cubic (BCC)

Atoms located at the eight corners, and one at the center of the cube Equivalent of one atom from the eight corners, and one atom at the center 2 atoms in a unit cell Co-ordination number : 8
4 1/8 s ahead 4 1/8 s behind Total 8 neighbors

Hard-Sphere Model

Body-Centered Cubic (BCC)

3a

a
2a

BCC Atomic Packing Factor

Unit cell c ontains: 1 + 8 x 1/8 = 2 atoms/unit cell

APF = 0.68

Face-Centered Cubic (FCC)

Atoms located at the eight corners, and the centers of all the cube faces Corner atom is shared among eight unit cells, facecentered atoms among two unit cells 4 atoms in a unit cell Co-ordination number : 12

Face-Centered Cubic (FCC)

FCC Atomic Packing Factor

Unit cell c ontains: 6 x 1/2 + 8 x 1/8 = 4 atoms/unit cell

APF = 0.74

FCC Stacking Sequence

ABCABC... Stacking Sequence 2D Projection B A sites B sites C sites A B C B

C B

B C B B

FCC Unit Cell

A B C

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Hexagonal Close Packed Structure (HCP)

Atoms located at top and bottom hexagonal faces, and at center of the faces 3 atoms provided by the plane between the two faces 6 atoms in a unit cell Ideal c/a ratio 1.633 Co-ordination number : 12 APF : 0.74

Hexagonal Close-Packed Structure (HCP)

ABAB... Stacking Sequence

3D Projection
A sites
c

2D Projection
Top layer Middle layer Bottom layer

B sites
A sites
a
Adapted from Fig. 3.3(a), Callister & Rethwisch 4e.

Coordination # = 12 6 atoms/unit cell APF = 0.74 c/a = 1.633

ex: Cd, Mg, Ti, Zn

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Energy and Packing

Interparticle Energy
Typical bond length

r0

Interatomic spacing
Typical energy

Dense, regular-packed structures tend to have lower energy

Interparticle Energy

r0

Interatomic spacing

Typical energy

Theoretical Density ()

Copper FCC Structure, A = 63.5 g/mol, r=0.128 nm = 0.128 * 10-7 cm n=4 (since FCC structure)

4(atoms/unit cell) * 63.5 (g/mol) 16 2 * (0.128 *10 7 ) 3 (cm 3 / unit cell ) * 6.023 *10 23 (atoms/mol)

8.89 g / cm3

(Compare with 8.94 g/cm3 which is the experimental value)

Common Densities for Materials

Why such A change?

Ceramic Crystal Structures

More complex than metals since two or more elements present Bonding can vary from purely ionic to purely covalent, and many in between If dominantly ionic bonding, crystal structures have electrically charged ions instead of atoms Cations positively charged (lost electrons) Anions negatively charged (gained electrons)

Factors that Determine the Ceramic Crystal Structure

1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.

Adapted from Fig. 3.4, Callister & Rethwisch 4e.

unstable 2. Maintenance of Charge Neutrality :

--Net charge in ceramic should be zero. --Reflected in chemical formula:

stable

stable Ca 2+ + cation Fanions F-

CaF 2 :

A m Xp
m, p values to achieve charge neutrality
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Co-ordination number and ion size ratio

Co-ordination number increases with rcation / ranion (c/a)

Computation of Minimum Cation-Anion Radius Ratio

Determine minimum rcation/ranion for an octahedral site (C.N. = 6) 2ranion + 2rcation = 2a

a 2ranion

2ranion + 2rcation = 2 2ranion ranion + rcation = 2ranion rcation = ( 2 - 1)ranion

rcation = 2 - 1 = 0.414 ranion

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Bond Hybridization
Bond Hybridization is possible when there is significant covalent bonding hybrid electron orbitals form For example for SiC

XSi = 1.8 and XC = 2.5

% ionic character = 100 {1- exp[-0.25(X Si - X C )2 ]} = 11.5%

~ 89% covalent bonding Both Si and C prefer sp3 hybridization Therefore, for SiC, Si atoms occupy tetrahedral sites

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Common Ceramic Crystal Structures

Structure Name Rock salt (sodium chloride) Cesium chloride Zinc blende Flourite Perovskite Spinel Structure Type AX Anion Packing FCC Cation co-ord # 6 Anion co-ord # 6 Examples

NaCl, MgO, FeO CsCl ZnS, SiC CaF2, UO2 BaTiO3 MgAl2O4

AX AX AX2 ABX3 AB2X4

Simple cubic FCC Simple cubic FCC FCC

8 4 8 12, 6 4,6

8 4 4 6 4

Example Problem: Predicting the Crystal Structure of FeO

On the basis of ionic radii, what crystal structure would you predict for FeO? Cation Ionic radius (nm) Al 3+ 0.053 Fe 2+ 0.077 Fe 3+ 0.069 Ca 2+ 0.100 Anion O2Cl F-

Answer:

rcation 0.077 = ranion 0.140 = 0.550

based on this ratio, -- coord # = 6 because

0.140 0.181 0.133

0.414 < 0.550 < 0.732 -- crystal structure is NaCl

Data from Table 3.4, Callister & Rethwisch 4e. 31

Rock Salt Structure

Same concepts can be applied to ionic solids in general. Example: NaCl (rock salt) structure
rNa = 0.102 nm rCl = 0.181 nm

rNa/rCl = 0.564
cations (Na+) prefer octahedral sites

Adapted from Fig. 3.5, Callister & Rethwisch 4e.

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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

Since 0.732 < 0.939 < 1.0, cubic sites preferred

Adapted from Fig. 3.6, Callister & Rethwisch 4e.

So each Cs+ has 8 neighbor Cl-

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AX2 Crystal Structures

Fluorite structure
Calcium Fluorite (CaF2) Cations in cubic sites UO2, ThO2, ZrO2, CeO2 Antifluorite structure positions of cations and anions reversed
Adapted from Fig. 3.8, Callister & Rethwisch 4e.
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ABX3 Crystal Structures

Perovskite structure

Ex: complex oxide BaTiO3

Adapted from Fig. 3.9, Callister & Rethwisch 4e.

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Density computation - Ceramics

Theoretical density of a crystalline ceramic

n (AC AA ) VC N A
'

n = number of formula units (all ions that are included in the chemical formula) within the unit cell AC = sum of atomic weights of all cations in the formula unit AA = sum of atomic weights of all anions in the formula unit Vc = unit cell volume NA = avogadros number = 6.023 * 1023 formula units/mol

Theoretical density of Sodium chloride

Compute theoretical density of NaCl ANa = 22.99 g/mol; ACl = 35.45 g/mol Ionic radii of Na+ = 0.102 nm, that of Cl- = 0.181 nm
a Na+

Cl-

.See the solution in the text book

Polymorphism and Allotropy

Polymorphism some metals and non metals have more than one crystal structure

Prevailing crystal structure depends on temperature and pressure

Polymorphism in elemental solids is called Allotropy

Carbon polymorphs as Diamond and Graphite Pure ion has a BCC crystal structure at room temperature and FCC at 912oC