What is the difference between atomic
structure and crystal structure?
Chapter 6
METAL STRUCTURE
ENT 145 Materials Engineering
Materials and Packing
Crystalline materials...
• atoms are situated in a repeating/
periodic array.
• typical of: -metals
-many ceramics
-some polymers
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline
Unit Cells
• subdivide the structure into small repeat entities
• represent the symmetry of crystal structures- all atom position
In the crystal may be generated by translation of the unit cells
along each of its edges
• basic structural unit or building block
Hard sphere model
Aggregate of atoms
Atomic structure relates to the number of protons and
neutrons in the nucleus of an atom, as well as the
number and probability distributions of the constituent
electrons.
Crystal structure pertains to the arrangement of atoms
in the crystalline solid material.
Chapter 3 - 1 Chapter 3 - 2
Metallic Crystal Structures
• Tend to be densely packed.
• Reasons for dense packing:
- Typically, only one element is present, so all atomic
radii are the same.
crystalline SiO2
Adapted from Fig. 3.23(a), - Metallic bonding is not directional.
Callister & Rethwisch 8e.
- Nearest neighbor distances tend to be small in
Si Oxygen order to lower bond energy.
- Electron cloud shields cores from each other
• Have the simplest crystal structures.
We will examine three such structures...
noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.
Chapter 3 - 3 Chapter 3 - 4
Simple Cubic Structure (SC)
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.
• Coordination # = 6
(# nearest neighbors)
Adapted from Fig. 3.2, Click once on image to start animation
Callister & Rethwisch 8e. (Courtesy P.M. Anderson)
Chapter 3 - Chapter 3 - 6
1
 Atomic Packing Factor (APF) Body Centered Cubic Structure (BCC)
Volume of atoms in unit cell* • Atoms touch each other along cube diagonals.
APF = --Note: All atoms are identical; the center atom is shaded
Volume of unit cell differently only for ease of viewing.
*assume hard spheres ex: Cr, W, Fe (), Tantalum, Molybdenum
• APF for a simple cubic structure = 0.52 • Coordination # = 8

volume
atoms atom
a 4
unit cell 1 p (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell Click once on image to start animation
Adapted from Fig. 3.2,
Callister & Rethwisch 8e.
contains 8 x 1/8 =
(Courtesy P.M. Anderson)
1 atom/unit cell 2 atoms/unit cell: 1 center + 8 corners x 1/8
Adapted from Fig. 3.24,
Callister & Rethwisch 8e. Chapter 3 - 7 Chapter 3 - 8

Exercise 1. Show for the body-centered cubic (BCC) crystal

Atomic Packing Factor: BCC structure that the unit cell edge length a and the atomic radius R
• APF for a body-centered cubic structure = 0.68 are related through a =4R / √3 .
3a
Using the triangle NOP
a (NP)2 = a2 + a2 = 2a2
And then for triangle NPQ,
2a (NQ) 2 = (QP) 2 + (NP) 2
But NQ = 4R, R being the atomic radius.
Close-packed directions: Also, QP = a. Therefore,
Adapted from R length = 4R = 3 a (4R)2 = a2 + 2a2
Fig. 3.2(a), Callister &
Rethwisch 8e.
a
or
atoms volume a = 4R / √3
4
unit cell 2 p ( 3a/4 ) 3
3 atom
APF =
3 volume
a
unit cell Chapter 3 - 9 Chapter 3 - 10

Face Centered Cubic Structure (FCC) Atomic Packing Factor: FCC

• APF for a face-centered cubic structure = 0.74
• Atoms touch each other along face diagonals. maximum achievable APF
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing. Close-packed directions:
ex: Al, Cu, Au, Pb, Ni, Pt, Ag length = 4R = 2 a
• Coordination # = 12 2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister & atoms volume
Rethwisch 8e. 4
unit cell 4 p ( 2a/4 ) 3
3 atom
Adapted from Fig. 3.1, Callister & Rethwisch 8e. APF =
Click once on image to start animation volume
(Courtesy P.M. Anderson) 4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8 a3
unit cell
Chapter 3 - 11 Chapter 3 - 12

2
 Theoretical Density, r Theoretical Density, r

Mass of Atoms in Unit Cell

• Ex: Cr (BCC)
Density = r = A = 52.00 g/mol
Total Volume of Unit Cell
R = 0.125 nm
nA
r = n = 2 atoms/unit cell
VC NA
R
Adapted from
Fig. 3.2(a), Callister &
a a = 4R/ 3 = 0.2887 nm
Rethwisch 8e.
where n = number of atoms/unit cell atoms
A = atomic weight g
unit cell 2 52.00 rtheoretical = 7.18 g/cm3
VC = Volume of unit cell = a3 for cubic mol
NA = Avogadro’s number r= ractual = 7.19 g/cm3
= 6.022 x 1023 atoms/mol a3 6.022 x 1023
volume atoms
Chapter 3 - 15
unit cell mol Chapter 3 - 16

Exercise 2.
Iron has a BCC crystal structure, an atomic radius of 0.124 nm,
and an atomic weight of 55.85 g/mol. Compute and compare its
theoretical density with the experimental value found in the
front section of the book.

Chapter 3 - 17 Chapter 3 - 18

Exercise 3.
Rhodium has an atomic radius of 0.1345 nm and a density of
12.41 g/cm3. Determine whether it has an FCC or BCC crystal
structure.

Chapter 3 - 19 Chapter 3 - 20

3
 Densities of Material Classes Polycrystalline Anisotropic
In general Graphite/ • Most engineering materials are polycrystalline.
rmetals > rceramics > rpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum
B ased on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W Adapted from Fig. K,
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
color inset pages of
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
Callister 5e.
(Fig. K is courtesy of
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
Paul E. Danielson,
Teledyne Wah Chang
• often large atomic masses Tin, Zinc
Zirconia Albany)
r (g/cm3 )

5
Ceramics have... 4
Titanium
Al oxide
1 mm
• less dense packing 3
Diamond
Si nitride
Aluminum
• often lighter elements Glass -soda
Concrete
Silicon PTFE
Glass fibers
GFRE*
2
Polymers have... Magnesium G raphite
Silicone
Carbon fibers
CFRE*
• Nb-Hf-W plate with an electron beam weld. Isotropic
PVC A ramid fibers
• low packing density AFRE *
• Each "grain" is a single crystal.
PET
1 PC
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O) • If grains are randomly oriented,
Composites have...
0.5 Wood overall component properties are not directional.
0.4
• intermediate values 0.3
• Grain sizes typically range from 1 nm to 2 cm
Data from Table B.1, Callister & Rethwisch, 8e.
(i.e., from a few to millions of atomic layers).
Chapter 3 - 21 Chapter 3 - 22

Various stages in the solidification of polycrystalline

Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa
Data from Table 3.3,
-Properties vary with Callister & Rethwisch
8e. (Source of data is
direction: anisotropic. R.W. Hertzberg,
Deformation and
-Example: the modulus Fracture Mechanics of
Engineering Materials,
of elasticity (E) in BCC iron: 3rd ed., John Wiley and
Sons, 1989.)

Small crystallite nuclei Growth of the crystallite E (edge) = 125 GPa

• Polycrystals
-Properties may/may not 200 mm Adapted from Fig.
4.14(b), Callister &
vary with direction. Rethwisch 8e.
(Fig. 4.14(b) is courtesy
-If grains are randomly of L.C. Smith and C.
Brady, the National
oriented: isotropic. Bureau of Standards,
Washington, DC [now
(Epoly iron = 210 GPa) the National Institute of
Standards and
-If grains are textured, Technology,
anisotropic. Gaithersburg, MD].)

Upon completion of solidification, grains having Grain structure as it would appear

irregular shapes have formed under microscope
Chapter 3 - 24

Polymorphism Crystal Systems

• Two or more distinct crystal structures for the same Unit cell: smallest repetitive volume which
material (allotropy/polymorphism)
contains the complete lattice pattern of a crystal.
iron system
titanium
liquid
, -Ti 7 crystal systems
1538ºC
BCC -Fe
carbon
1394ºC 14 crystal lattices
diamond, graphite
FCC -Fe
912ºC
BCC -Fe a, b, and c are the lattice constants

Fig. 3.4, Callister & Rethwisch 8e.

Chapter 3 - 25 Chapter 3 - 26

4
 Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2 ½½½

000
y
a b
Point coordinates for unit cell
x  corner are 111
z 2c

Translation: integer multiple of
  lattice constants  identical
b y position in another unit cell
b
Chapter 3 - Chapter 3 - 28

Point Coordinates
Point Coordinates

tableun_03_p57

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

x [uvw]

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a
negative index
families of directions <uvw>
figun_03_p58
Chapter 3 - 31

5
 Crystallographic Planes Crystallographic Planes
• Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions &
common multiples. All parallel planes have
same Miller indices.

• Algorithm
1. If the plane passes through selected origin, either
another parallel plane must be constructed within
the unit cell or new origin must be construct.
2. Read off intercepts of plane with axes in
terms of a, b, c
3. Take reciprocals of intercepts
4. Reduce to smallest integer values
5. Enclose in parentheses, no commas i.e., (hkl) Adapted from Fig. 3.10,
Callister & Rethwisch 8e.
Chapter 3 - 33 Chapter 3 - 34

Crystallographic Planes Crystallographic Planes

z
example a b c z
1. Intercepts 1 1  c
example a b c c
2. Reciprocals 1/1 1/1 1/ 1. Intercepts 1/2 1 3/4 
1 1 0
3. Reduction 1 1 0 y 2. Reciprocals 1/½ 1/1 1/¾
a b 2 1 4/3  y
4. Miller Indices (110) 
x 3. Reduction 6 3 4 a b
z x
example a b c 4. Miller Indices (634)
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0 Family of Planes {hkl}
y
4. Miller Indices (100) a b
x Ex: {100} = (100), (010), (001), (100), (010), (001)
Chapter 3 - 35 Chapter 3 - 36

X-Ray Diffraction X-Rays to Determine Crystal Structure

• Incoming X-rays diffract from crystal planes.

reflections must
be in phase for
a detectable signal
extra  Adapted from Fig. 3.20,
q q
distance
Callister & Rethwisch 8e.
travelled
by wave “2” spacing
dhkl between
planes

Braggs Law
n
dhkl =  = wavelength
• Diffraction gratings must have spacings comparable to 2 sin q
the wavelength of diffracted radiation. dhkl = Interplanar spacing
a
• Can’t resolve spacings   dhkl =
a= lattice parameter
√h2 + k2 + l2
• Spacing is the distance between parallel planes of n = order of reflection
atoms.
Chapter 3 - 37 Chapter 3 - 38

6
 Exercise 3.
X-Ray Diffraction Pattern Using the data for molybdenum in Table 3.1, compute
z z z
c c c the interplanar spacing for the (111) set of planes

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

x x x (211)

(200)

Diffraction angle 2q

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.22, Callister 8e.

Chapter 3 - 39 Chapter 3 - 40

Exercise 4.
Determine the expected diffraction angle for the first-
order reflection from the (113) set of planes for FCC
platinum when monochromatic radiation of wavelength
0.154 nm is used.

Chapter 3 - 41 Chapter 3 - 42

SUMMARY
• Atoms may assemble into crystalline or
amorphous structures.
• Common metallic crystal structures are FCC, BCC, and
HCP. Coordination number and atomic packing factor
are the same for both FCC and HCP crystal 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).
• Crystallographic points, directions and planes are
specified in terms of indexing schemes.
Crystallographic directions and planes are related
to atomic linear densities and planar densities.

Chapter 3 - 43 Chapter 3 - 44

7
 SUMMARY ANNOUNCEMENTS
Reading:
• Materials can be single crystals or polycrystalline.
Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals Core Problems:
with randomly oriented grains.
• Some materials can have more than one crystal
structure. This is referred to as polymorphism (or Self-help Problems:
allotropy).
• X-ray diffraction is used for crystal structure and
interplanar spacing determinations.

Chapter 3 - 45 Chapter 3 - 46