The Structure of Crystalline Solids

Chapter 3 -
 INTRODUCTION
• From Chapter 2, atomic bonding, which are determined by
the electron structures of the individual atoms.

• The present discussion is devoted to the next level of the

structure of materials, specifically, to some of the
arrangements that may be assumed by atoms in the solid
state.

• Within this framework, concepts of crystallinity and

noncrystallinity are introduced. For crystalline solids the
notion of crystal structure is presented, specified in terms
of a unit cell.
Chapter 3 - 2
 INTRODUCTION
• The three common crystal structures found in metals are
then detailed, along with the scheme by which
crystallographic points, directions, and planes are
expressed.

• Single crystals, polycrystalline materials, and non-

crystalline materials are considered. Another section of this
chapter briefly describes how crystal structures are
determined experimentally using x-ray diffraction
techniques.

Chapter 3 - 3
 FUNDAMENTAL CONCEPTS

• Solid materials may be classified according to the regularity with

which atoms or ions are arranged with respect to one another.

• A crystalline material is one in which the atoms are situated in a

repeating or periodic array over large atomic distances; that is, long-
range order exists, such that upon solidification, the atoms will
position themselves in a repetitive three-dimensional pattern, in
which each atom is bonded to its nearest-neighbor atoms.

Chapter 3 - 4
 FUNDAMENTAL CONCEPTS
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.23(a),
Callister & Rethwisch 8e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.

Chapter 3 - 5
Packing of crystals:
Non dense =random
Dense = regular

Chapter 3 - 6
 Unit cell and lattice parameters

• Unit cell : small repeated

entities
• It is the basic structural unit or
building block of the crystal
structure
• Its geometry is defined in
terms of 6 lattice parameters:
3 edges length (a, b, c)
3 interaxial angles

Chapter 3 - 7
 Unit cell and lattice parameters
• Unit cells for most crystal structures are parallelepipeds or
prisms having three sets of parallel faces; one is drawn
within the aggregate of spheres.
• A unit cell is chosen to represent the symmetry of the
crystal structure, wherein all the atom positions in the
crystal may be generated by translations of the unit cell
integral distances along each of its edges.
• More than a single unit cell may be chosen for a particular
crystal structure; however, we generally use the unit cell
having the highest level of geometrical symmetry.

Chapter 3 - 8
Unit cell parameters

Chapter 3 - 9
 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.
- 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
• Have the simplest crystal structures.

We will examine three such structures...

Chapter 3 - 10
 Metallic Crystal Structures

• 3 crystal structures:
– Face-Centered Cubic FCC
– Body-Centered Cubic BCC
– Hexagonal close-packed HCP

• Characterization of Crystal structure:

– Number of atoms per unit cell
– Coordination number (Number of nearest
neighbor or touching atoms)
– Atomic Packing Factor (APF) : what fraction of
the cube is occupied by the atoms
Chapter 3 - 11
 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)

Click once on image to start animation

(Courtesy P.M. Anderson)

Chapter 3 - 12
 The Face-Centered Cubic Crystal
Structure
• A unit cell of cubic geometry, with atoms located at each of the corners
and the centers of all the cube faces.

• Each corner atom is shared among eight unit cells, whereas a face-
centered atom belongs to only two.

• Therefore, one-eighth of each of the eight corner atoms and one-half of

each of the six face atoms, or a total of four whole atoms, may be
assigned to a given unit cell.

• Corner and face positions are really equivalent; that is, translation of the
cube corner from an original corner atom to the center of a face atom will
not alter the cell structure.
Chapter 3 - 13
 The Face-Centered Cubic Crystal
Structure
• In metals, each atom has the same number of nearest-
neighbor or touching atoms, called coordination number.
• For face-centered cubic, the coordination number is 12.
• Front face atom has four corner nearest-neighbor atoms
surrounding it, four face atoms that are in contact from
behind, and four other equivalent face atoms residing in the
next unit cell to the front.

Chapter 3 -
 The Face-Centered Cubic Crystal
Structure

• For the FCC structure, the

atomic packing factor is 0.74,
which is the maximum.

Chapter 3 - 15
 Face Centered Cubic Structure (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

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

• Coordination # = 12

Adapted from Fig. 3.1, Callister & Rethwisch 8e.

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

Chapter 3 - 16
 Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2 a
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
APF =
3 volume
a
unit cell
Chapter 3 - 17
The Face-Centered Cubic Crystal
Structure

Chapter 3 - 18
 APF = 0.74 solve ?
Relation between r and a

Chapter 3 - 19
 The Body-Centered Cubic Crystal
Structure
• A cubic unit cell with atoms located at all eight corners and a single atom
at the cube center.

• Two atoms are associated with each BCC unit cell: the equivalent of one
atom from the eight corners, each of which is shared among eight unit
cells, and the single center atom, which is wholly contained within its
cell.

• The coordination number for the BCC crystal structure is 8; each center
atom has as nearest neighbors its eight corner atoms.

• Because the coordination number is less for BCC than FCC, so also is the
atomic packing factor for BCC lower—0.68 versus 0.74.
Chapter 3 - 20
 The Body-Centered Cubic Crystal
Structure

• Coordination no. = 8

• Number of atoms per unit

cell = 2
• what fraction of the cube is
occupied by the atoms or
Atomic packing factor

Chapter 3 - 21
The Body-Centered Cubic Crystal
Structure

Chapter 3 - 22
 APF = 0.68 solve ?
Relation between r and a

Chapter 3 - 23
The Hexagonal Close-Packed Crystal
Structure

Chapter 3 - 24
 HCP

• The coordination number and APF

for HCP crystal structure are same
as for FCC: 12 and 0.74,
respectively.

• HCP metal includes: cadmium,

magnesium, titanium, and zinc.

Chapter 3 - 25
 HCP
• c/a ratio is 1.633

• The top and bottom faces of the unit cell consist of six atoms that
form regular hexagons and surround a single atom in the center.
• Another plane that provides three additional atoms to the unit cell
is situated between the top and bottom planes.
• The equivalent of six atoms is contained in each unit cell; one-
sixth of each of the 12 top and bottom face corner atoms, one-half
of each of the 2 center face atoms, and all 3 midplane in-terior
atoms.

Chapter 3 - 26
 Theoretical Density, r

Mass of Atoms in Unit Cell

Density = r =
Total Volume of Unit Cell

nA
r =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.022 x 1023 atoms/mol

Chapter 3 - 27
 Theoretical Density, r
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
Adapted from
Fig. 3.2(a), Callister &
a a = 4R/ 3 = 0.2887 nm
Rethwisch 8e.
atoms
g
unit cell 2 52.00 rtheoretical = 7.18 g/cm3
mol
r= ractual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol Chapter 3 - 28
 Densities of Material Classes
In general Graphite/
rmetals > rceramics > rpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum
Based on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

r (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
• less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda
• often lighter elements Concrete
Silicon PTFE
Glass fibers
GFRE*
2 Carbon fibers
Polymers have... Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1 HDPE, PS
(often amorphous) PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3

Data from Table B.1, Callister & Rethwisch, 8e.
Chapter 3 - 29
 Crystals as Building Blocks
• Some engineering applications require single crystals:
-- diamond single -- turbine blades
crystals for abrasives Fig. 8.33(c), Callister &
Rethwisch 8e. (Fig. 8.33(c)
(Courtesy Martin Deakins,
courtesy of Pratt and
GE Superabrasives,
Whitney).
Worthington, OH. Used with
permission.)

• Properties of crystalline materials

often related to crystal structure.
-- Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)

Chapter 3 - 30
 Polycrystals Anisotropic
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
1 mm

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

• Each "grain" is a single crystal.
• If grains are randomly oriented,
overall component properties are not directional.
• Grain sizes typically range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Chapter 3 - 31
 Single vs Polycrystals
• Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
E (diagonal) = 273 GPa
Data from Table 3.3,
Callister & Rethwisch
8e. (Source of data is
R.W. Hertzberg,
Deformation and
Fracture Mechanics of
Engineering Materials,
3rd ed., John Wiley and
Sons, 1989.)
200 mm Adapted from Fig.
4.14(b), Callister &
Rethwisch 8e.
(Fig. 4.14(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].)
Chapter 3 - 32
 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

Chapter 3 - 33
 Crystal Systems
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

Fig. 3.4, Callister & Rethwisch 8e.

Chapter 3 - 34
 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 - 35
 Crystallographic Directions
z pt. 2
Example 2:
head
pt. 1 x1 = a, y1 = b/2, z1 = 0
pt. 2 x2 = -a, y2 = b, z2 = c

y
pt. 1:
x tail => -2, 1/2, 1

Multiplying by 2 to eliminate the fraction

-4, 1, 2 => [ 412 ] where the overbar represents a

negative index

families of directions <uvw>

Chapter 3 - 36
 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>
Chapter 3 - 37
 Linear Density
Number of atoms
• Linear Density of Atoms  LD = Unit length of direction vector

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

# atoms
a 2
LD = = 3.5 nm-1
Adapted from
Fig. 3.1(a),
length 2a
Callister &
Rethwisch 8e.

Chapter 3 - 38
 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] a
a1
2
Adapted from Fig. 3.8(a),
Callister & Rethwisch 8e.
a2 -a3
2

ex: ½, ½, -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
Chapter 3 - 39
 HCP Crystallographic Directions
• Hexagonal Crystals
– 4 parameter Miller-Bravais lattice coordinates are
related to the direction indices (i.e., u'v'w') as
follows.
z

[ u 'v 'w ' ]  [ uvtw ]

1
u = (2 u ' - v ')
3
a2
1
v = (2 v ' - u ')
- 3
a3
t = - (u +v )
w = w'
a1

Fig. 3.8(a), Callister & Rethwisch 8e.

Chapter 3 - 40
 Crystallographic Planes

Adapted from Fig. 3.10,

Callister & Rethwisch 8e.
Chapter 3 - 41
 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. Read off 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 i.e., (hkl)

Chapter 3 - 42
 Crystallographic Planes
z
example a b c
1. Intercepts 1 1  c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
Chapter 3 - 43
 Crystallographic Planes
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)

Chapter 3 - 44
 Crystallographic Planes (HCP)
• In hexagonal unit cells the same idea is used
z

example a1 a2 a3 c
1. Intercepts 1  -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1 a2

3. Reduction 1 0 -1 1
a3

4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.8(b),

Callister & Rethwisch 8e.

Chapter 3 - 45
 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.

Chapter 3 - 46
 Virtual Materials Science & Engineering (VMSE)
• VMSE is a tool to visualize materials science topics such as
crystallography and polymer structures in three dimensions

• Available in Student Companion Site at www.wiley.com/college/callister

Chapter 3 - 47
and in WileyPLUS
 VMSE: Metallic Crystal Structures &
Crystallography Module
• VMSE allows you to view crystal structures, directions, planes,
etc. and manipulate them in three dimensions

Chapter 3 - 48
 Unit Cells for Metals
• VMSE allows you to view the unit cells and manipulate
them in three dimensions

• Below are examples of actual VMSE screen shots

FCC Structure HCP Structure

Chapter 3 - 49
VMSE: Crystallographic Planes Exercises

Additional practice on indexing crystallographic planes

Chapter 3 - 50
 Planar Density of (100) Iron
Solution: At T < 912ºC iron has the BCC structure.
2D repeat unit

(100) 4 3
a= R
3

Adapted from Fig. 3.2(c), Callister & Rethwisch 8e. Radius of iron R = 0.1241 nm
atoms
2D repeat unit 1
1 atoms atoms
19
Planar Density = = 2 = 12.1 = 1.2 x 10
area a2 4 3 nm 2 m2
R
2D repeat unit 3
Chapter 3 - 51
 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
nm 2 m2
area 16 3 2
R
2D repeat unit 3
Chapter 3 - 52
 VMSE Planar Atomic Arrangements
• VMSE allows you to view planar arrangements and rotate
them in 3 dimensions

BCC (110) Plane

Chapter 3 - 53
 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.
Chapter 3 - 54
 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
d between
planes

Measurement of X-ray
n
critical angle, qc, intensity d=
(from 2 sin qc
allows computation of
detector)
planar spacing, d.
q
qc
Chapter 3 - 55
 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 2q

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.22, Callister 8e.

Chapter 3 - 56
 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 - 57
 SUMMARY

• 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
with randomly oriented grains.
• Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).
• X-ray diffraction is used for crystal structure and
interplanar spacing determinations.

Chapter 3 - 58
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 3 - 59
Polymorphism

Chapter 3 - 60
Crystallographic Points,
Directions, and Planes

Chapter 3 - 61
 POINT COORDINATES

Point position Z
specified in terms
of its coordinates 1,1,1
as fractional
multiples of the
unit cell edge 0,0,0
Y
lengths
( i.e., in terms of X
a b and c)

Chapter 3 - 62
Solve point coordinates (2,3,5,9)

Chapter 3 - 63
solution

Chapter 3 - 64
 Crystallographic directions
1- A vector of convenient length is positioned such that
it passes through the origin of the coordinate system.
Any vector may be translated throughout the crystal
lattice without alteration, if parallelism is maintained.
2. The length of the vector projection on each of the
three axes is determined; these are measured in
terms of the unit cell dimensions a, b, and c.
3. These three numbers are multiplied or divided by a
common factor to reduce them to the smallest
integer.
4. The three indices, not separated by commas, are
enclosed as [uvw]. The u, v, and w integers
correspond to the reduced projections along x, y, and
z axes, respectively.
Chapter 3 - 65
Example

Chapter 3 - 66
Solution

Chapter 3 - 67
 Z

[0 1 0]
[1 0 1]

Chapter 3 - 68
 Planes ( miller indices)

1- If the plane passes through the selected origin, either another parallel plane
must be constructed within the unit cell by an appropriate translation, or a
new origin must be established at the corner of another unit cell.

2. At this point the crystallographic plane either intersects or parallels each of

the three axes; the length of the planar intercept for each axis is determined
in terms of the lattice parameters a, b, and c.

3. The reciprocals of these numbers are taken. A plane that parallels an axis
may be considered to have an infinite intercept, and, therefore, a zero index.

4. If necessary, these three numbers are changed to the set of smallest integers
by multiplication or division by a common factor.

5. Finally, the integer indices, not separated by commas, are enclosed within
parentheses, thus: (hkl).

Chapter 3 - 69
example

Chapter 3 - 70
Solution

Chapter 3 - 71
 Example : solve

X
Chapter 3 - 72
 solve

z
c

z
y
c a b

x
 y

a b
x Chapter 3 - 73
 Crystallographic Planes
z
example a b c
1. Intercepts 1 1  c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
Chapter 3 - 74
 Crystallographic Planes
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

Chapter 3 - 75
Chapter 3 - 76