16-01-10

Chapter 3: Structures of Metals & Ceramics

the crystalline solid state

topics:

CHAPTER 3

ISSUES TO ADDRESS...

unit cell (3.3)

What is the difference in atomic arrangement

between crystalline and noncrystalline solids?

metallic crystal structures (3.4)

density computa4ons metallic/ceramic (3.5)

What features of a metals/ceramics atomic

structure determine its density?

ceramic crystal structures, densi4es and

crystal systems (3.6, 3.7, 3.11)

direc4ons,
planes (3.13-3.14)

How do the crystal structures of ceramic

materials differ from those for metals?
Under what circumstances does a material
property vary with the measurement direction?

ctromagne4c

a4on

Equa4on
certainty Principle

bers

als

anics & Atomic

Atoms

4es

Energy and Packing

Non dense, random packing

Materials and Packing

Crystalline materials...

Energy

atoms pack in periodic, 3D arrays

typical neighbor
bond length
typical neighbor
bond energy
Dense, ordered packing

typical of:
r

-metals
-many ceramics
-some polymers

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

Energy
Noncrystalline materials...

typical neighbor
bond length

Oxygen

atoms have no periodic packing

occurs for:

typical neighbor
bond energy

Si

-complex structures
-rapid cooling

"Amorphous" = Noncrystalline

Dense, ordered packed structures tend to have

lower energies.

noncrystalline SiO2
Adapted from Fig. 3.41(b),
Callister & Rethwisch 4e.

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Unit cell
The unit cell is the minimum repea2ng unit necessary to generate the en2re
crystal upon applica2on of suitable transla2on, rota2on, mirror, or inversion
opera2ons.

Preferred because it displays

the maximum symmetry of
the structure.

La7ce
point

Metallic Crystal Structures

Metallic Crystal Structures

How can we stack metal atoms to minimize
empty space (in 2-dimensions)?
Staggered (90.7%)
Lined Up (78.5%)

Tend to be densely packed.

Reasons for dense packing:

- Typically, only one element is present, so all atomic

radii are the same.
- Metallic bonding is not directional.
- Nearest neighbor distances tend to be small in
order to lower bond energy.
- Electron cloud shields cores from each other

vs.

Metals have the simplest crystal structures.

We will examine three such structures...

Now stack these 2-D layers to make 3-D structures

7

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Cubic packing

Cubic crystal structures

Face centered
cubic (fcc)
(bcc) cubic (bcc)
Simple Cubic Simple Cubic
Face centered
cubic Body
(fcc) centered
Body ccubic
entered

An ion in the body of a cell belongs en2rely to that cell and counts as 1.

a = length of unit cell

BCC

SC
1

# of atoms in cell

CoordinaBon #

An ion on an edge is shared by four cells and hence contributes .

12

Filling FracBon

74 %

68%

52%

An ion at a vertex is shared by eight cells, and so contributes .

RelaBon

2a = 4r

3a = 4r

a = 2r

An ion on a face is shared by two cells and contributes .

r = radius of atom
FCC

Simple Cubic Structure (SC)

Rare due to low packing density (only Po
Close-packed directions are cube edges.

Body Centered Cubic Structure (BCC)

has this structure)

Atoms touch each other along cube diagonals.

--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

Coordination # = 6
(# nearest neighbors)

ex: Cr, W, Fe (), Tantalum, Molybdenum

Coordination # = 8

Click once on image to start animation

Click once on image to start animation

(Courtesy P.M. Anderson)

(Courtesy P.M. Anderson)

11

Adapted from Fig. 3.2,

Callister & Rethwisch 4e.

2 atoms/unit cell: 1 center + 8 corners x 1/8

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4 )3

16-01-10

atomic packing factor, SC

Face Centered Cubic Structure (FCC)

Atoms touch each other along face diagonals.

volume of atoms in unit cell

APF =

--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

volume of unit cell

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

Coordination # = 12
volume / atom
atoms / unit cell

R = a
a

APF =

1 (4/3)(0.5a)3
a3
volume / unit cell

Adapted from Fig. 3.1, Callister & Rethwisch 4e.

Click once on image to start animation
(Courtesy P.M. Anderson)

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

a
a

APF for a simple cubic structure = 0.52

13

atomic packing factor, BCC

Atomic packing factor, FCC

volume of atoms in unit cell

APF =

volume of unit cell

volume / atom
R

atoms / unit cell

a

3a

APF =
a

2 (4/3)( 3 a/4)3
a3
volume / unit cell

2a
Close-packed direc4ons:

APF for a simple cubic structure = 0.68

3 a/4

length = 4R = 3 a
volume
atom
volume
unit cell

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theore2cal density,

#atoms / unit cell

Theoretical Density,
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell

atomic weight
(g / mol)

n A
VC NA

volume / unit cell

(cm3 / unit cell)

R
Avogadros number
6.02 1023 atoms / mol

Adapted from
Fig. 3.2(a), Callister &
Rethwisch 4e.

2 52.00

unit cell

unit cell exercise

Nickel crystallizes in a fcc laFce. Its density is 8.90 g/cm3. What is the atomic
radius of nickel in pm? Show all work.
Nickel: fcc unit cell

Atomic mass: 58.69 g for 1 mol of Ni atoms

2d = 4r

In FCC unit cell the face diagonal ( 2 d) = 4r

a = 4R/ 3 = 0.2887 nm

atoms

a 3 6.022 x 1023

g
mol

theoretical

= 7.18 g/cm3

actual

= 7.19 g/cm3

volume

atoms

unit cell

mol
18

characteris2cs of selected elements at 20C

Element
Aluminum
Argon
Barium
Beryllium
Boron
Bromine
Cadmium
Calcium
Carbon
Cesium
Chlorine
Chromium
Cobalt
Copper
Flourine
Gallium
Germanium
Gold
Helium
Hydrogen

Symbol
Al
Ar
Ba
Be
B
Br
Cd
Ca
C
Cs
Cl
Cr
Co
Cu
F
Ga
Ge
Au
He
H

At. Weight
(amu)
26.98
39.95
137.33
9.012
10.81
79.90
112.41
40.08
12.011
132.91
35.45
52.00
58.93
63.55
19.00
69.72
72.59
196.97
4.003
1.008

Density
(g/cm3)
2.71
-----3.5
1.85
2.34
-----8.65
1.55
2.25
1.87
-----7.19
8.9
8.94
-----5.90
5.32
19.32
-----------

Atomic radius
(nm)
0.143
-----0.217
0.114
----------0.149
0.197
0.071
0.265
-----0.125
0.125
0.128
-----0.122
0.122
0.144
-----------

Adapted from
Table, "Characteristics of
Selected
Elements",
inside front
cover,
Callister 6e.

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Example Problem

Example Problem

Polonium is the only metal that forms a simple

cubic crystal structure. Use the fact that the
density if 9.32 g/cm3 to calculate its atomic
radius.

Europium forms a body-centered cubic unit cell

and has a density of 4.68 g/cm3. Determine the
length of the edge of the cubic cell.

Atomic Bonding in Ceramics

Ceramic Crystal Structures

Bonding:

-- Can be ionic and/or covalent in character.

-- % ionic character increases with difference in
electronegativity of atoms.

Oxide structures
oxygen anions larger than metal cations
close packed oxygen in a lattice (usually FCC)
cations fit into interstitial sites among oxygen ions

Degree of ionic character may be large or small:

CaF2: large
SiC: small

Adapted from Fig. 2.7, Callister & Rethwisch 4e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition. Copyright 1939 and 1940, 3rd edition copyright 1960 by Cornell University.
23

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Ionic structures

Factors that Determine Crystal Structure

1. Relative sizes of ions Formation of stable structures:

CHARGE NEUTRALITY

--maximize the # of oppositely charged ion neighbors.

Net charge in the structure should be zero.

Ca2+ +
cation

CaF2 :

General form:

F-

unstable

anions

stable

2. Maintenance of
Charge Neutrality :

F-

--Net charge in ceramic

should be zero.
--Reflected in chemical
formula:

AmXp

CaF 2 :

Adapted from Fig. 3.4,

Callister & Rethwisch 4e.

stable

Ca 2+
cation

F-

anions
F-

A m Xp

m, p determined by charge neutrality

m, p values to achieve charge neutrality

26

structure of ionic solids: rock salt

Coordination Number and Ionic Radii

r
Coordination Number increases with

Na+ Cl-

cation
r anion

To form a stable structure, how many anions can

surround around a cation?
r cation
r anion
< 0.155

Coord.
Number
linear
2
triangular

0.155 - 0.225

0.225 - 0.414

4 tetrahedral

0.414 - 0.732

6 octahedral

0.732 - 1.0

Adapted from Table 3.3,

Callister & Rethwisch 4e.

cubic

ZnS
(zinc blende)
Adapted from Fig. 3.7,
Callister & Rethwisch 4e.

NaCl
(sodium
chloride)

Adapted from Fig. 3.5,

Callister & Rethwisch 4e.

CsCl
(cesium
chloride)
Adapted from Fig. 3.6,
Callister & Rethwisch 4e.
27

rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564

caBons (Na+) prefer

octahedral sites

(6, 6) CoordinaBon

Can be seen as a fcc laFce of anions, where ca2ons occupy the octahedral holes.
A unit cell contains 4 Na+ ions and 4 Cl- ions. Ions touch along the cell edge.

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CsCl

MgO and FeO

Cs+Cl
-

MgO and FeO also have the NaCl structure

O2-

rO = 0.140 nm

Mg2+

rMg = 0.072 nm

(8, 8)
CoordinaBon

rMg/rO = 0.514

rCs+ 0.170
rcl- 0.181

cations prefer octahedral sites

rCs+
rCl

0.170
= 0.939
0.181

Since 0.732 < 0.939 < 1.0,

cubic sites preferred

The structure can be described in terms of interpenetra2ng cubic units of

Cs+ and Cl-, where Cs+ ions occupy all the cubic holes in a simple cubic array
of Cl- ions (or vice versa).

Adapted from Fig. 3.5,

Callister & Rethwisch 4e.

So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms

A unit cell contains 1 Cs+ ion and 1 Cl- ion. Ions touch along the body diagonal.
29

Zinc blende structure

FCC with half of
the tetrahedral
posi2ons lled.
Both Anions and
Ca2ons
tetrahedrally
coordinated
Example: GaAs,
many other III-V
semiconductors

Other compounds with this structure: CsCl, CsBr, CsI, and NH4Cl

ourite structure (CaF2)

Ca4ons lie in an expanded fcc array and the F-

ions occupy the two types of tetrahedral
holes.

A unit cell contains 4 Ca2+ and 8 F- ions.

Ions touch along the body diagonal.

Ca2+ F-

Examples: UO2, ThO2, ZrO2, CeO2

(8, 4) CoordinaBon

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density computa2on - ceramics

Example Problem: Predicting the Crystal

Structure of FeO
On the basis of ionic radii, what crystal structure
would you predict for FeO (AX type)?
Cation

Ionic radius (nm)

Al 3+

0.053

Fe 2 +

0.077

Fe 3+

0.069

Ca 2+

0.100

O 2-

# formula units within a unit cell

Answer:

rcation 0.077
=
ranion 0.140
= 0.550

based on this ratio,

-- coord # = 6 because

Anion

0.181

F-

0.133

n' ( AC + AA)
VC NA
Avogadros number
6.02 1023 atoms / mol

volume / unit cell

(cm3 / unit cell)

0.414 < 0.550 < 0.732

0.140

Cl -

Sum of atomic weights of all

cations + anions in the formula unit
(g / mol)

-- crystal structure is NaCl

Data from Table 3.4,
Callister & Rethwisch 4e.
33

Silicate ceramics
Zn2+ S2-
=

n' ( AC + AA)
VC NA

AC = AZn = 65.41 g/mol

AA = AS = 32.06 g/mol
r + r = (3/4) a
S
Zn= (4/3)
a
(0.074 + 0.184) 10-7 cm

(4, 4) CoordinaBon

r(Zn2+) = 0.074 nm

(65.41+ 32.06)

(0.597 10-7)3 (6.02 1023 )

= 3.05 g/cm3

The actual density is 4.1 g/cm3, since the covalent character in ZnS reduces the

distance between Zn and S compared to the predicted one based on pure ionic
bonding.

Most common elements on earth are Si & O

Si4+
O2length of the body diagonal = 4 x (RZn2+ + RS2-)
crystobalite
length of the body diagonal = 4 x (0.074nm + 0.184nm)
length of the body diagonal = 1.028 nm
a = 0.597 nm

Adapted from Figs. 3.10-11,

Callister & Rethwisch 3e

SiO2 (silica) polymorphic forms are quartz, crystobalite, & tridymite

The strong Si-O bonds lead to a high mel2ng temperature (1710oC) for this
material
Bonding of adjacent SiO44- accomplished by the
sharing of common corners, edges, or faces
Presence of ca2ons such as Ca2+, Mg2+, & Al3+
1. maintain charge neutrality, and
2. ionically bond SiO44- to one another

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glass structure

Single vs Polycrystals
SINGLE CRYSTALS

BASIC UNIT:
4-

SiO 4 tetrahedron
Si 4+
2 -

GLASS is noncrystalline (amorphous)

Fused silica is SiO2 to which no impuri2es have been added

Other common glasses contain impurity ions such as
Na+, Ca2+, Al3+, and B3+

E (diagonal) = 273 GPa

-Example: the modulus

of elas2city (E) in BCC iron:
E (edge) = 125 GPa

POLYCRYSTALS
QUARTZ is crystalline SiO2:

Na +
Si 4+

Silicate
glass
tetrahedro
n SiO4

O2 -

(soda glass)

Data from Table 3.7, Callister &

Rethwisch 3e. (Source of data is
R.W. Hertzberg, Deformation and
Fracture Mechanics of Engineering
Materials, 3rd ed., John Wiley and
Sons, 1989.)

-Proper2es vary with

direc2on: anisotropic.

-Proper2es may/may not

vary with direc2on.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.

200 mm

Adapted from Fig. 3.41, Callister & Rethwisch 3e.

Adapted from Fig. 5.19(b), Callister & Rethwisch 3e.

(Fig. 5.19(b) is courtesy of L.C. Smith and C. Brady, the National Bureau of Standards,
Washington, DC [now the National Institute of Standards and Technology, Gaithersburg, MD].)a

unit cell

crystal systems

UNIT CELL

The size and shape of the unit cell can be

described by three la7ce vectors:

Based on shape of unit cell

Unit cell = 3-dimensional
unit that repeats in space

a, b, c

Unit cell geometry

completely specied by a,
b, c & , , (laJce
parameters or laJce
constants)

and interaxial angles:

, ,

CUBIC CRYSTAL SYSTEM

7 crystal systems
14 crystal la7ces

a = b = c

= = = 90

Cubic crystal systems

way of describing unit cells
general

; a b c
Cubic

= = = 90
a = b = c

Seven possible
combina2ons of a, b, c & ,
, , resul2ng in seven
crystal systems
Compare table 3.6

10

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Dened as line between two points: a vector

Steps for nding the 3 indices deno2ng a direc2on

crystallographic direc2ons (1)

crystallographic
direc2ons (2)
Determine the point posi2ons of a beginning point (X1 Y1 Z1) and a

ending
point
(X2 Y2 Z2) for direc2on, in terms of unit cell edges
Determine the indices
for these
direcBons

THE CRYSTALLOGRAPHIC DIRECTION INDICES [U, V, W]

The vector of the direcBon resolved along each of the coordinate axes and
reduced to the smallest integers.

ASSIGNMENT

1. Vector reposi2oned (if necessary) to pass

through origin.
2. Read o projec2ons in terms of
unit cell dimensions a, b, and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
5. If any of the indices is nega2ve, a bar is
placed in top of that index

y
x

[uvw]

Calculate dierence between ending and star2ng point

Mul2ply the dierences by a common constant to convert them to the
smallest possible integers
u, v, w
[2
The three indices are not separated by commas and are enclosed in
square brackets: [uvw]
If any of the indices is nega2ve, a bar is placed in top of that index

FAMILY OF DIRECTIONS

Due to the symmetry of crystal structures the spacing and arrangement of atoms may
be the same in several direcBons. These are known as equivalent direcBons. A group
of equivalent direcBons is known as a family of direcBons. Families of direcBons are
wriZen in angular brackets.

EXAMPLE

< 100 > [100],[010],[001],[010],[001],[100]

1, 0,

< 111 > [111],[11 1 ],[1 1 1],[ 1 11], [ 1 1 1 ],[ 1 1 1],[ 1 1 1 ],[1 1 1 ]

=> 2, 0, 1 => [ 201 ]

-1, 1, 1 =>

where overbar represents a negative index

[ 111 ]

< 110 > [110],[011],[101],[1 1 0],[01 1 ],[10 1 ], [ 1 1 0],[0 1 1 ],[ 1 0 1 ],[ 1 10],[0 1 1],[ 1 01]

crystallographic planes (1)

crystallographic planes (2)

MILLER INDICES Reciprocals of the (three) axial intercepts for a plane, cleared of
fracBons & common mulBples. All parallel planes have same Miller indices.

Planes that are crystallographically equivalent have the same atomic packing
.All parallel planes have same Miller indices.

z
c

y
a
x

1. Read o intercepts of plane with axes in terms of a, b, c

2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no commas.

(hkl)

a

Intercepts

Reciprocals

1/

1/

1/

Reduc2on

Miller indices

(200)

11

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crystallographic planes (3)

crystallographic planes (4)

Determine the Miller indices of planes A, B, and C.

Construct the (110) Crystallographic plane.

plane

Miller indices

z
c

(110)

Reciprocals

1/1

1/1

1/

Intercepts

y
a

(c) 2003 Brooks/Cole Publishing /

Thomson Learning

plane A

Intercepts

Reciprocals

1/1

1/1

1/1

Reduc2on

Miller indices

(111)

atomic arrangements

crystallography nota2on overview

The crystal structure will dictate the atomic arrangement for certain crystallographic planes.

FCC UNIT CELL WITH

(110) PLANE

Atomic packing dierent in the two cases

BCC UNIT CELL WITH

(110) PLANE

DIRECTION SQUARE [111]

BRACKETS
FAMILY OF DIRECTIONS ANGLE BRACKETS
< 111 > [111],[11 1 ],[1 1 1],[ 1 11], [ 1 1 1 ],[ 1 1 1],[ 1 1 1 ],[1 1 1 ]

PLANE PARANTHESES
(111)

FAMILY OF PLANES CURLY BRACKETS

{111} (111),(111 ),(1 1 1),( 1 11), ( 1 1 1 ),( 1 1 1), ( 1 1 1 ),(1 1 1 )

FAMILY OF PLANES Contains all the planes that are crystallographically equivalent,
i.e. have the same atomic packing.

{111} (111),(111 ),(1 1 1),( 1 11), ( 1 1 1 ),( 1 1 1), ( 1 1 1 ),(1 1 1 )

12