Chapter 3

Structures of Metals and Ceramics

 Chapter 3

X-ray Diffraction
 Structures of Metals and Ceramics

Issues to Address...

• How do atoms assemble into solid structures?

• How do the structures of ceramic
materials differ from those of metals?
• How does the density of a material depend on
its structure?
• When do material properties vary with the
sample (i.e., part) orientation?
 Reading and Thinking

• What is Lattice, Unit Cell?

• What is Metallic Structures (SC, BCC, FCC, HCP)?
• Ionic Crystals
• Miller-Bravais Indices
• Seven Crystal System
• X-ray diffraction
 Metallic Crystals

• Tend to be densely packed.

• Have several 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.

• Have the simplest crystal structures.

We will look at three such structures...

 Unit Cells

Three dimensional array of points coinciding

Lattice
with atom positions (lattice points).

Lattice point Positions in the structure which are identical.

Smallest and convenient repeat unit in the

Unit cell lattice.
 Simple Cubic (SC) Structure

• Rare due to low packing density (only Po has this structure)

• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)

1 atoms/unit cell: 8 corners x 1/8

 Atomic Packing Factor

Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
4
a unit cell 1 (0.5a)3
3
R = 0.5a APF =
a3 volume
close-packed directions unit cell
 Body Centered Cubic (BCC) Structure

• Atoms touch each other along cube diagonals.

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

• Coordination # = 8

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

 Atomic Packing Factor : BCC

• APF for a body-centered cubic structure = 0.68

3a

2a

Close-packed directions:
R length = 4R = 3 a
a
atoms volume
4 3
unit cell 2 ( a )
3 4 atom
APF =
3 volume
a
unit cell
 Face Centered Cubic (FCC) Structure

• Atoms touch each other along face diagonals.

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

• Coordination # = 12

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

 Atomic Packing Factor : FCC

• APF for a face-centered cubic structure = 0.74

maximum achievable APF
Close-packed directions:
length = 4R = 2a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
atoms volume
4 2 3
unit cell 4 3 ( a ) atom
4
APF =
volume
a3
unit cell
 FCC Stacking Sequence

• ABCABC... Stacking Sequence

• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C
 Hexagonal Close-Packed (HCP) Structure

• ABAB... Stacking Sequence

• 3D Projection • 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633
 Metallic Structure : HCP

8
2 × R
c c 3
= = 1.633
a 2R

4 3
πr × 2
APFHCP = 3 = 74 %
3
8 2R
a2
a1
120°
Number of nearest atoms = 12
 Theoretical Density_1

Mass of Atoms in UnitCell

Density =  =
Total Volume of UnitCell

nA
 =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.023 x 1023 atoms/mol
 Theoretical Density_2

• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R a = 4R/ 3 = 0.2887 nm
a
atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol
 Usage of Density

Comparing X-ray density with bulk density

can check if there are vacant atom sites or

extra atoms (interstitials).

 Characteristics of Selected Elements at 20℃
At. Weight Density Crystal Atomic radius
Element Symbol (amu) (g/cm3) Structure (nm)
Aluminum Al 26.98 2.71 FCC 0.143
Argon Ar 39.95 ------ ------ ------
Barium Ba 137.33 3.5 BCC 0.217
Beryllium Be 9.012 1.85 HCP 0.114
Boron B 10.81 2.34 Rhomb ------
Bromine Br 79.90 ------ ------ ------
Cadmium Cd 112.41 8.65 HCP 0.149
Calcium Ca 40.08 1.55 FCC 0.197
Carbon C 12.011 2.25 Hex 0.071
Cesium Cs 132.91 1.87 BCC 0.265
Chlorine Cl 35.45 ------ ------ ------
Chromium Cr 52.00 7.19 BCC 0.125
Cobalt Co 58.93 8.9 HCP 0.125
Copper Cu 63.55 8.94 FCC 0.128
Flourine F 19.00 ------ ------ ------
Gallium Ga 69.72 5.90 Ortho. 0.122
Germanium Ge 72.59 5.32 Dia. cubic 0.122
Gold Au 196.97 19.32 FCC 0.144
Helium He 4.003 ------ ------ ------
Hydrogen H 1.008 ------ ------ ------
Adapted from [Link]
[Link]
 Densities of Material Classes

Graphite/
metals? ceramics? polymers Metals/
Alloys
Ceramics/ Polymers
Composites/
fibers
Semicond
Why? 30
Based on data in Table B1, Callister
Platinum
Metals have... 20 Gold, W
Tantalum
*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
• close-packing Epoxy composites (values based on
60% volume fraction of aligned fibers
(metallic bonding) 10 Silver, Mo
Cu,Ni
in an epoxy matrix).

• large atomic mass Steels

 (g/cm3)
Tin, Zinc
Zirconia
Ceramics have... 5
Titanium
4 Al oxide
• less dense packing Diamond
Si nitride
3
(covalent bonding) Aluminum Glass-soda
Concrete
Glass fibers
Silicon PTFE
• often lighter elements 2 Magnesium Graphite
GFRE*
Carbon fibers
Silicone CFRE*
Polymers have... PVC
PET
Aramid fibers
AFRE*
• poor packing 1 PC
HDPE, PS
PP, LDPE
(often amorphous)
• lighter elements (C,H,O) 0.5
Wood
Composites have... 0.4
0.3
• intermediate values Data from Table B1, Callister 6e.
 Ceramic Bonding

• Bonding:
--Mostly ionic, some covalent.
--% ionic character increases with difference in
electronegativity.

• Large vs small ionic bond character:

CaF2 : large

SiC : small
 Ionic Bonding & Structure

• Charge Neutrality:
--Net charge in the F-
structure should CaF2: Ca2+ +
cation anions
be zero.
F-

--General form: AmXp

m, p determined by charge neutrality
• Stable structures:
--maximize the # of nearest oppositely charged neighbors.

Unstable Stable Stable

 Coordination No. and Ionic Radii

rcation
• Coordination # increases with ranion
Issue: How many anions can you
arrange around a cation?
 Predicting Structure of FeO

• On the basis of ionic radii, what crystal structure

would you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al3+ 0.053 rcation 0.077
=
Fe2+ 0.077 ranion 0.140
Fe3+ 0.069 = 0.550
Ca2+ 0.100
based on this ratio,
--coord # = 6
Anion
--structure = NaCl
O2- 0.140
Cl- 0.181
F- 0.133
 Structure Of Compounds: NaCl

• Compounds: Often have similar close-packed structures.

• Structure of NaCl • Close-packed directions

--along cube edges.
 AmXp Structures

rcation 0.100
• Consider CaF2 : = ≈ 0.8
ranion 0.133
• Based on this ratio, coord # = 8 and structure = CsCl.
• Result: CsCl structure w/only half the cation sites
occupied.
• Only half the cation sites
are occupied since
#Ca2+ ions = 1/2 # F- ions.
 Diamond and Perovskite Structure

Diamond structure Perovskite structure

 Heating and Cooling of an Iron Wire

α-Fe (BCC) 912℃ γ -Fe (FCC)

The same atoms

• Demonstrates "polymorphism"
can have more
than one crystal
structure.
1536

1391

912
 Polymorphism

• Two or more distinct crystal structures for the same

material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538ºC
BCC -Fe
carbon
diamond, graphite 1394ºC
FCC -Fe
912ºC
BCC -Fe
 Crystal Systems_1

Unit cell: smallest repetitive volume which

contains the complete lattice pattern of a crystal.

7 crystal systems

14 crystal lattices

a, b, and c are the lattice constants

Crystal Systems_2

(P, B, F)

(P)

(P, B)

(P)

(P, B, F, B)

(P, B)

(P)
 Five Symmetrical Plane Lattices

(a) Parallelogram (b) Square (c) Rhombus

(d) Rectangle (e) Diamond

 Seven Crystal Systems

Seven crystal systems : based on crystal symmetry

Cubic - four 3 fold mutually at 70°

Hexagonal - one 6 fold

Trigonal - one 3 fold (pulled out cubic along diagonal of cubic)

Tetragonal - one 4 fold (pulled out cubic along one edge)

Orthorhombic - three mutually perpendicular 2 fold

Monoclinic - one 2 fold

Triclinic - none
 Point Coordinates

z
111 Point coordinates for unit cell
c center are

a/2, b/2, c/2 ½½½

000
y
a b
x  Point coordinates for unit cell
z corner are 111
2c


  Translation: integer multiple of

y lattice constants  identical
b
position in another unit cell
b
 Crystallographic Directions

z Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of unit cell
y dimensions a, b, and c.
3. Adjust to smallest integer values.
x 4. Enclose in square brackets, no commas
[uvw].

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a negative
index
 HCP Crystallographic Directions

z
Algorithm
1. Vector repositioned (if necessary) to
pass through origin.
2. Read off projections in terms of unit
a2 cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
-
a3 [uvtw]
a2
a1
a2 -a3
2

ex: ½, ½, -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
 Three Index to Four Index Conversion (HCP)

For hexagonal system (uvtw), t = -(u+v)

Conversion from the three-index system to four-index system
[u´v´w´] → [uvtw]

n
u = (2u ' - v')
3
n
v = ( 2 v' - u ' )
3
t = - ( u + v)
w = nw '
 Example : Crystallographic Directions

Direction [uvw], Family of directions <uvw>

Example  110 
[110][101] [011][110 ][110 ][101] [233] 2
- 11
3 [111]
[101][ 011][ 011][ 011][110 ][101] [100]

[001]
[100]
c
<110> : Face diagonal
[010] [120]
<111> : Cube diagonal 1
1 0
b 2
<100> : Cube edge
[210]
a
[100]
[120]
Crystallographic Planes_1
 Crystallographic Planes_2

z
example a b c
1. Intercepts 1 1 c
2. Reciprocals
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts c
2. Reciprocals
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (200) a b
x
 Crystallographic Planes_3

z
example a b c c
1. Intercepts 1/2 1 3/4 
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3  y

3. Reduction 6 3 4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)

 Crystallographic Planes (HCP)

• In hexagonal unit cells the same idea is used

z

example a1 a2 a3 c
1. Intercepts -1 1
2. Reciprocals -1 1
a2
1 0 -1 1
3. Reduction 1 0 -1 1
a3

4. Miller-Bravais Indices (1011) a1

 Crystallographic Directions and Planes

In cubic system, planes are perpendicular to direction.

It does not apply for other systems.
For cubic system,
A×B
cos θ =
A B

For example,
(111), (100)

1×1 + 1× 0 + 1× 0
cos θ =
12 + 12 + 12 • 12 + 0 2 + 0 2
1
=
3

∴ θ = 54 . 74 °

cf) directions included in a plane

 Close Packed Structure - FCC

FCC : ABCABCABC……

(111)

[111]

A A
C
B B
A A A
C C
B
A A

Stacking of (111) Planes

 Close Packed Structure - HCP

HCP : ABABABAB……
[001]

(001)
A-
A A

B B
(002)
A A A B-

B
A A
(001)
A-

Stacking of (002) planes

 Linear Density

Number of atoms
• Linear Density of Atoms  LD =
Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
Ex) Linear density of Al in [110] direction
a = 0.405 nm
a = 0.405 nm

# atoms
a 2
LD   3.5 nm 1
length 2a
 Crystallographic Planes

• We want to examine the atomic packing of

crystallographic planes

• Iron foil can be used as a catalyst. The atomic

packing of the exposed planes is important.

a) Draw (100) and (111) crystallographic planes for

Fe.
b) Calculate the planar density for each of these
planes.
 Planar Density of (100) Iron

Solution: At T < 912C iron has the BCC structure.

2D repeat unit

(100) 4 3
a R
3

Radius of iron R = 0.1241 nm

atoms
2D repeat unit 1
1 atoms
= = 12.1 = 1.2 x 1019 atoms
Planar Density = 2 2
area a 4 3 nm2 m2
R
2D repeat unit 3
 Planar Density of (111) Iron

Solution (cont): (111) plane 1 atom in plane/ unit surface cell

2a atoms in plane
atoms above plane
atoms below plane

3
h a
2
2
 4 3  16 3 2
area  2 ah  3 a  3 
2
R÷
÷  R
atoms  3  3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
area 16 3 2
nm 2 m2
R
2D repeat unit 3
 X-Ray Diffraction

• Diffraction gratings must have spacings comparable to the

wavelength of diffracted radiation.
• Can’t resolve spacings  
• Spacing is the distance between parallel planes of atoms.
 X-Rays to Confirm Crystal Structure

• Incoming X-rays diffract from crystal planes.

de
te
ct

??
or

in r a
s

co ys
ay
reflections must

X-
r

m
be in phase to
X-

??
in
detect signal

??
g

g
in
extra
g o 
?? t
distance Adapted from Fig.
travelled  ou  3.2W, Callister 6e.
by wave ?? spacing
d between
planes

• Measurement of: x-ray

Critical angles, qc, intensity d=n/2sinc
(from
for X-rays provide
detector)
atomic spacing, d.

c
 Crystalline and Noncrystalline Materials

X-ray diffraction
: advantages in X-rays for crystal structure analysis
wavelength 0.1~10 Å which is comparable to crystal lattice

Bragg’s law : λ = 2d sinθ

 Diffractometer Measurement

.
Uses monochromic X - ray Cu Kα (1.5418 A )

a
Cubic system d hkl =
h 2 + k 2 + l2

θ : variable , a : lattice constant

 Simple Cubic

all {hkl}

{100} {110} {111} {200} {210} {211} {220} {221}

h2 + k2 + l2 = 1, 2, 3, 4, 5, 6, 8, 9
 BCC

h2 + k2 + l2 must be even for diffraction.

{110} {200} {211} {220} {310} {222}

h2 + k2 + l2 = 2, 4, 6, 8, 10, 12

Out of phase !! ∴ (100) in BCC does not appear

 X-Ray Diffraction Pattern

z z z
c c c

y (110) y y
a b a b a b
Intensity (relative)

x x x (211)

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

 Importance of X-Ray Diffraction

difference in CsCl and BCC : (100) peak exists but weak

a3

a1 a2

Cs+ Cl-
 FCC

hkl all even or all odd (unmixed indices)

{111} {200} {220} {311} {222} {400} {331}

h2 + k2 + l2 = 3, 4, 8, 11, 12, 16, 19
 X-Ray Diffraction

Further Thinking !

1. X-Ray System
2. How can we get single λ ?
3. Diffraction Order
4. SC vs BCC
5. Alloying Effect
6. Why Powder ?
7. Lattice Parameter Measurement
8. Peak Separation (Phase Transformation)
 Materials and Packing

Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
• long range order
Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
• short range order
 Energy and Packing

• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, regular packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, regular-packed structures tend to have

lower energy.
 Noncrystalline Solids

• Basic Unit: • Glass is amorphous

4- • Amorphous structure
Si04 tetrahedron occurs by adding impurities
Si4+ (Na+,Mg2+,Ca2+, Al3+)
O2-
• Impurities:
interfere with formation of
crystalline structure.

• Quartz is crystalline
Na+
SiO2:
Si4+
O2-

(soda glass)

Adapted from Fig. 12.11, Callister, 6e.

 Polycrstals

• Most engineering materials are polycrystals.

1 mm Adapted from Fig. K, color inset

pages of Callister 6e.
(Fig. K is courtesy of Paul E.
Danielson, Teledyne Wah Chang
Albany)

• Nb-Hf-W plate with an electron beam weld.

• Each "grain" is a single crystal.
• If crystals are randomly oriented,
overall component properties are not directional.
• Crystal sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
 Crystalline and Noncrystalline Materials

(1) Polycrystal

grain boundary

single grain

(2) Anisotropy
direction of properties
function of symmetry
amorphous material → isotropic
 Single VS Polycrystals

• Single Crystals E (diagonal) = 273 GPa

-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not 200 mm
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
 Summary

• Atoms may assemble into crystalline or

amorphous structures.
• We can predict the density of a material,
provided we know the atomic weight, atomic
radius, and crystal geometry (e.g., FCC,
BCC, HCP).
• Material properties generally vary with single
crystal orientation (i.e., they are anisotropic),
but properties are generally non-directional
(i.e., they are isotropic) in polycrystals with
randomly oriented grains.