CHAPTER 3: STRUCTURE OF

CRYSTALLINE SOLIDS
• Crystalline – repetitive 3-D structure
- all metals, many ceramics and
some polymers

• Atomic Hard Sphere Model

represent atoms as solid spheres touching
each other.

• Lattice
3-D array of points coinciding with atom
positions
 METALLIC CRYSTAL STRUCTURE
• Tend to be densely packed.
-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.
Types: 1) FCC 2) BCC 3) HCP
Focus on the unit cell: smallest repetitive entity
Properties :
•Coordination number – number of nearest neighbor or touching atoms
•Atomic Packing Factor (APF) – ratio of volume of atoms in unit cell
to the total unit cell volume
FACE CENTERED CUBIC STRUCTURE
(FCC)
• Atom at each corner, and at center of each face.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

• Coordination # = 12
ATOMIC PACKING FACTOR: FCC
• APF for a face-centered cubic structure = 0.74

a
BODY CENTERED CUBIC STRUCTURE
(BCC)
• Atom at each corner, and at the center of cube.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

• Coordination # = 8
ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68

R
a
 HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

B sites Middle layer

A sites Bottom layer

• Coordination # = 12
• APF = 0.74
 FCC STACKING SEQUENCE
• ABCABC... Stacking Sequence
• 2D Projection
A
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C
HCP APF
a  2R
2
c  2 a  1.633a
3

• APF = 0.74
 THEORETICAL DENSITY, 

# atoms/unit cell Atomic weight (g/mol)

 nA
Volume/unit cell Vc N A Avogadro's number
(cm 3 /unit cell) (6.023 x 10 23 atoms/mol)
 Example: Density Computation

Example: Compute the theoretical density of Copper

Data from Table inside front cover of Callister (see next slide):

• crystal structure = FCC: 4 atoms/unit cell

• atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
-7
• atomic radius R = 0.128 nm (1 nm = 10 cm)
Vc = a 3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10 -23 cm 3

Result: theoretical Cu = 8.89 g/cm 3

Compare to actual: Cu = 8.94 g/cm 3

 Characteristics of Selected Elements at 20C
At. Weight Density Crystal Atomic radius
Element Symbol (amu) (g/cm 3 ) 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 ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ ------ teristics of
Cadmium Cd 112.41 8.65 HCP 0.149 Selected
Elements",
Calcium Ca 40.08 1.55 FCC 0.197 inside front
Carbon C 12.011 2.25 Hex 0.071 cover,
Callister 6e.
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 ------ ------ ------
 Polymorphism and Allotropy
Polymorphism
-Having more than one crystal structure (change with T & P)
-Ex. Low-Carbon Steel can exist as BCC or FCC
Temperature, C
Liquid
1536
BCC Stable
1391
longer
heat up
FCC Stable
shorter!
914 longer!
BCC Stable
cool down
Tc 768 magnet falls off
shorter

Allotropy
-Polymorphism in elemental solid
-Ex. Carbon can exist as graphite or diamond
 SUMMARY

• Atoms may have crystalline or amorphous

structures.
• We can predict the density of a material from the
atomic weight, atomic radius, and crystal
structure (e.g., FCC, BCC, HCP).

• Anisotropic material - properties vary with

direction – true for a for a single crystal
orientation.
• Isotropic material - properties are non-
directional – true for polycrystals with randomly
oriented grains.
Crystal Systems
Unit Cell:

Parameters:
a , b, c ,  ,  , 

7 Crystal Systems:
-Cubic
-Hexagonal
-Tetragonal
-Orthorhombic
-Rhombohedral
-Monoclinic
-Triclini
 Crystallographic Positions (Coordinates)
- Coordinates of points expressed as fractions of unit cell
dimensions
 Crystallographic Directions
-defined by line between two points

Steps:
1. Translate vector to pass at origin.
2. Determine lengths of components
(projections) in terms of unit cell
dimensions.
3. Multiply or divide by a common factor
to reduce to smallest possible integer
values, uvw.
4. Direction: [uvw]

Family of Directions – nonparallel directions which are equivalent

(same atom spacing).
Ex. Cubic: <100> family – [100], [010], [001]
Tetragonal <100> - [100], [010]
 Crystallographic Planes (Miller Indices)

Steps:
1. If the plane passes through origin, translate origin.
2. Determine lengths of planar intercepts in terms of unit
cell dimensions.
3. Take reciprocals of the numbers in Step 2.
4. Multiply or divide by a common factor to reduce to
integers: hkl
5. Enclose: (hkl)

Example:
Planes for Hexagonal Crystals
Four axes: 1 , 2 ,  3 , z

Example:
Linear Density
– fraction of the length of the line intersected by atoms.
Planar Density
- Fraction of the area occupied by atoms (count atoms only if
plane intersect its center.
Example: For simple cubic crystal, find:
1. Linear density for [111] direction,
2. Planar density for (100) plane.
Textbook Definitions:

LD =

PD =
X-RAYS TO CONFIRM CRYSTAL STRUCTURE
• Incoming X-rays diffract from crystal planes.
de
te c
to

”
r

“1
i n ra y
s
co s
X-
y reflections must
r- a
m
be in phase to
in

”
X

“2
g
detect signal

“1
g

”
extra
oi
n 
“2
distance tg Adapted from Fig. 3.2W,
 u 
”
travelled o Callister 6e.
by wave “2” spacing
d between
planes

• Measurement of: x-ray

Critical angles, c, intensity d=n /2sin c
(from
for X-rays provide
detector)
atomic spacing, d.

c
 a
For cubic crystal: d hkl 
h2  k 2  l 2
 Quiz Review

1. At the position equal to the

equilibrium spacing of two atoms,
which of the following is/are true?

A. The net force is equal to zero.

B. The net energy is maximum.
C. The net energy is zero.
D. A and B above.
2. Two atoms are at an interatomic
spacing less than the equilibrium
spacing.  Which of the following is
true regarding the atoms?
A. The net energy is minimum.
B. The new force is zero.
C. The attractive force is greater than
the repulsive force.
D. The attractive force is less than the
repulsive force.
3. The interatomic bond that is
formed by the transfer of one or
more electrons from one atom to the
other is called

A. Covalent bond.
B. Ionic bond.
C. Metallic bond.
D. Secondary bond.
4. An element with an atomic
number of 9 is

A. Inert
B. Electronegative
C. Electropositive
D. Transition metal
5. Two atoms of different metals
have the same crystal structure. If
Atom A has a bigger atomic radius
than atom B, which has the higher
atomic packing factor?
A. Atom A
B. Atom B
C. Depends on atomic weights
D. None of the above.
6. What is the coordination number
for a simple cubic crystal structure?

A. 12
B. 8
C. 6
D. 4
7. For which crystal system is are
the angles between the three axes
equal to 90o and two of the unit cell
dimensions are equal to each other?
A. Cubic
B. Tetragonal
C. Orthorhombic
D. Triclinic
8. Identify the crystallographic
direction of the vector:

A. [-1 1 1]
B. [1 1 -1]
C. [1 -1 1]
D. [1 1 1]
9. Identify the crystallographic
direction of the vector:
A. [-2 1 2]
B. [-2 1 1]
C. [1 -2 2]
D. [-1 2 1]
10. Identify the crystallographic
plane.

A. (-201)
B. (321)
C. (320)
D. (231)
11. Identify the crystallographic
plane.

A. (-3 1 -4)
B. (3 -1 2)
C. (2 1 2)
D. (3 0 2)
12. For an FCC crystal, along with
direction is the linear density
maximum?

A. [111]
B. [100]
C. [110]
D. [11-1]