Chapter 3: The Structure of Crystalline Solids

ISSUES TO ADDRESS...

• How do atoms assemble into solid structures?

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample (i.e., part) orientation?

Chapter 3 - 1
Basic Concepts:

Solid materials may be classified according to the

regularity with which the atoms or ions are
arranged:
a)Crystalline material
b)Non-crystalline material

Chapter 3 - 2
Crystalline material- one in which the atoms
are situated in a repeating or periodic
array over large atomic distances –
i.e., long- range order exists, such that
upon solidification, the atoms will
position themselves in a repetitive three-
dimensional pattern.

Chapter 3 - 3
 Materials and Packing
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" = or Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.23(b),
literally “without form” Callister & Rethwisch 8e.

Chapter 3 - 4
Chapter 3 - 5
 Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have

lower energies.
Chapter 3 - 6
Chapter 3 - 7
- All metals, many ceramic materials, and some
polymers form crystalline line structures under
normal solidification conditions.

Atomic hard-sphere model found in some metals

Chapter 3 - 8
- Some properties of crystalline solids depend
on the crystal structure of the material, the
manner in which atoms, ions, or molecules are
spatially arranged.
- Atomic hard-sphere model is one when
crystalline structures are thought of as being
solid spheres having well-defined diameters.
- The nearest-neighbor atoms touch one another

Chapter 3 - 9
Definition of terms:

• Unit Cell
-small repeat entities used in describing
crystal structures
- usually 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

Chapter 3 - 10
• Unit cell is the basic structural unit
defining the crystal structure by virtue of
its geometry and the atoms within.
• We will generally use the unit cell having
the highest level of geometrical
symmetry.

Chapter 3 - 11
  Metallic Crystal Structures
• How can we stack metal atoms to minimize
empty space?
2-dimensions

vs.

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

Chapter 3 - 12
 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: face-centered cubic,
body-centered cubic, and hexagonal close-packed, ...

Chapter 3 - 13
Atomic Radii and Crystal Structures

Chapter 3 - 14
 Face-Centered Cubic Crystal Structure
(FCC)
The crystal structure found for many metals has
a unit cell of cubic geometry, with atoms located
at each of the corners and centers of all the cube
faces
-Shows a hard-sphere model
For the FCC unit cell

Chapter 3 - 15
• The atom centers are represented by
small circles to provide a better
perspective on atom positions

Chapter 3 - 16
Chapter 3 - 17
 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 - 18
• Number of atoms per unit cell, N, can
be computed as:
N = Ni + Nf + NC
2 8
Where Ni = number of interior atoms
Nf = number of face atoms
NC = number of corner atoms

Chapter 3 - 19
• For FCC crystal structure, there are 8
corner atoms (NC = 8), 6 face atoms (Nf =
6), and no interior atoms (Ni = 0).
• Thus,
N=0 + 6 + 8
2 8
= 4 whole atoms may be assigned
to a given unit cell.

Chapter 3 - 20
Two other important characteristics of a crystal structure:
Coordination number

 Is the number of atoms touching a particular atom or

the number of nearest neighbors.
 It is an indication of how tightly and efficiently atoms
are packed together.
•The coordination number for FCC metals, CN = 12

Atomic Packing Factor (APF)

 The fraction of space occupied by atoms, assuming
that atoms are hard spheres.

Chapter 3 -
 Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
Length, a = 2R 2
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 3
unit cell 4 ( 2a/4)
3 atom
APF =
3 volume
a
unit cell
Chapter 3 - 22
 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

Chapter 3 - 23
 Sample Problem:
Calculate the volume of an FCC unit cell in terms
of the atomic radius R.
Given: FCC unit cell Req’d: Vc in terms of a
Soln:
V c = a3 ;
Vc = (2R √2)3 = 16 R3 √2 Ans.

Chapter 3 - 24
Sample Problem:
Show that the atomic packing factor for the FCC crystal
structure is 0.74
Given: FCC unit cell
Req’d: show that APF = 0.74
Sol’n:
APF = VT atoms in a unit cell .
V unit cell
APF = 4(4/3)  R3 =  .
16 R3 2 32
= 0.74
Chapter 3 - 25
Body Centered Cubic Structure (BCC)
• Another common metallic crystal structure
• Also has a cubic unit cell with atoms located at all
8 corners and a single atom at the cube center
• Center and corner atoms touch one another along
cube diagonals, and relationship of unit cell
length a and atomic radius R
a = 4R
√3

Chapter 3 - 26
 Body Centered Cubic Structure (BCC)
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

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

• Coordination # = 8

Adapted from Fig. 3.2,

Click once on image to start animation Callister & Rethwisch 8e.
(Courtesy P.M. Anderson)
2 atoms/unit cell: 1 center + 8 corners x 1/8
Chapter 3 - 27
 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
Adapted from R length = 4R = 3 a
Fig. 3.2(a), Callister &
Rethwisch 8e.
a
atoms volume
4
unit cell 2  ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell Chapter 3 - 28
Show for the body centered cubic crystal structure
that the unit cell edge length a and the atomic
radius R are related through a = 4R/3 .
Given: BCC
Req’d: show that a = 4R/3 4R

a2 a

Sol’n:

(4R)2 = a2 + (a2)2
16 R2 = 3 a2
R = a3 or a = 4R
4 3
Chapter 3 -
 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 - 30
Simple Cubic (SC) crystal structure

(a) A hard-sphere unit cell (b) a reduced-sphere unit cell

Chapter 3 - 31
 Atomic Packing Factor (APF)
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
a 4
unit cell 1 (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.24,
Callister & Rethwisch 8e. Chapter 3 - 32
Hexagonal Close-Packed Structure
(HCP)
- Consists of 6 atoms that form
regular hexagons and a single
atom in the center
- Another plane provides 3
additional atoms to the unit cell
is situated between the top and
bottom planes.
- Where a and c, respectively are
the short and long unit cell
dimensions

Chapter 3 - 33
 Hexagonal Close-Packed Structure
(HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a Adapted from Fig. 3.3(a),
Callister & Rethwisch 8e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 Chapter 3 - 34
 Summary of Crystal Structure

Atoms/ Coordination
Structure a vs R Cell No. APF
SC a = 2R 1 6 0.52
BCC a = 4R/  3 2 8 0.68
a = 4R/2
FCC a = 2R  2 4 12 0.74
a = 2R,
HCP c = 1.6333a 6 12 0.74

Chapter 3 -
 Density Computations
• Theoretical density, ρ = n A
Vc NA
• Where
n = number of atoms associated with each unit cell
A = atomic weight
VC = volume of unit cell
NA = Avogadro’s number (6.022 x 1023 atoms/mol)

Chapter 3 - 36
 Theoretical Density, 
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
Adapted from
a a = 4R/ 3 = 0.2887 nm
Fig. 3.2(a), Callister &
Rethwisch 8e.
atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol Chapter 3 - 37
 Copper has an atomic radius of 0.128 nm, an FCC crystal structure
and an atomic weight of 63.5 g/mol. Compute its theoretical
density and compare it with the measured density, 8.94 g/cm3.

Given: Copper; FCC crystal n = 4 atoms/cell

R = 0.128 nm = 1.28x10-8 cm Vc = a3
A = 63.5 g/mol Na = 6.023x1023 atoms/mol
Measured  = 8.94 g/cm3 a = 2R2 ; Vc = (2R 2)3 = 16R32
Req’d:  & compare w/ measured
Sol’n: = n A
= nA ;
.

162R3NA
Vc NA
= (4atoms/cell)(63.5g/mol)
16x2 x (1.28x10-8 cm)3
x (6.023x1023 atoms/mol)
= 8.887 g/cm3

Chapter 3 - 38
Determine the density of BCC iron, w/c has a lattice
parameter of 0.2866 nm. Compare the answer w/ the
measured density of 7.870 g/cm3.

Given: BCC Fe, a = 0.2866 nm, Meas.  = 7.87 g/cm3

Reqd:  and compare with meas. value
Soln:
 = n A ; n = 2 atoms/cell,
VC NA A = 55.85 g/mol
VC = a3

= 2 (55.85) .
(2.866x10-8)3(6.023x1023)
= 7.878 g/cm3 > meas. 

Chapter 3 - 39
 Densities of Material Classes
In general Metals/
Graphite/
Composites/
metals > ceramics > polymers Alloys
Ceramics/
Semicond
Polymers
fibers
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

 (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium Graphite
Silicone
Carbon fibers
CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1
(often amorphous) HDPE, PS
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 - 40
 Polymorphism and Allotropy
• Some metals, and nonmetals, may have more than
one crystal structure known as polymorphism
• Termed allotropy when found in elemental solids
• The prevailing crystal structure depends on both
the temperature and external pressure.
• Examples: graphite = stable at ambient conditions
diamond = is formed at high pressures
• pure iron – has BCC structure at room temp,
which changes to FCC iron at 912OC

Chapter 3 - 41
Examples

Gray tin

White tin

Chapter 3 - 42
 Problems
1. Show for the body centered cubic crystal structure that the
unit cell edge length a and the atomic radius R are related
through a = 4R/ .
2. Show that the APF for BCC = 0.68
3. On the basis of ionic radii, what crystal structure would
you predict for FeO?
• Hint: FeO is an AX type of compound, det. the cation-
anion radii ratio, rc/ra
4. On the basis of crystal structure, compute for the
theoretical density of NaCl.
5. The density of potassium w/c has the BCC structure &
one atom per lattice point is 0.855 g/cm3. The atomic
weight of potassium is 39.09 g/mol. Calc. a) lattice
parameter, b) atomic radius of potassium, in Å.
Chapter 3 - 43
CRYSTAL SYSTEMS

ISSUES TO ADDRESS...

• How to define points, directions, planes, as well as

linear, planar, and volume densities

– Define basic terms and give examples of each:

• Points (atomic positions

• Vectors (defines a particular direction - plane normal)
• Miller Indices (defines a particular plane)
• relation to diffraction
• 3-index for cubic and 4-index notation for HCP

Chapter 3 - 44
 Crystallographic Directions, and Planes

Now that we know how atoms arrange themselves to form

crystals, we need a way to identify directions and planes of
atoms.

Why?

•Deformation under loading (slip) occurs on certain

crystalline planes and in certain crystallographic directions.
Before we can predict how materials fail, we need to know what
modes of failure are more likely to occur.
•Other properties of materials (electrical conductivity,
thermal conductivity, elastic modulus) can vary in a crystal with
orientation.

Chapter 3 - 45
Crystallographic Directions, and Planes

Chapter 3 - 46
Crystal Systems – Some Definitional information

Unit cell: smallest repetitive volume which

contains the complete lattice pattern of a crystal.

7 crystal systems of varying

symmetry are known
These systems are built by changing
the lattice parameters:
a, b, and c are the axial or edge
lengths
, , and  are interaxial angles

14 crystal lattices

Fig. 3.4, Callister 7e.

Chapter 3 -
• Unit cell geometry: An x, y, z coordinate
system is established with its origin at one of
the unit cell corners
• Axial lengths a, b, c
• Interaxial angles α, β, γ
• Sometimes termed lattice parameters
• 7 different possible combinations of a, b, c,
and α, β, γ, each representing a distinct crystal
system

Chapter 3 - 48
 7 Crystal Systems

orthorhombic hexagonal
monoclinic trigonal
cubic tetragonal triclinic

Crystal System External Minimum Symmetry Unit Cell Properties

Triclinic None a, b, c, al, be, ga,

Monoclinic One 2-fold axis, || to b (b unique) a, b, c, 90, be, 90
Orthorhombic Three perpendicular 2-folds a, b, c, 90, 90, 90
Tetragonal One 4-fold axis, parallel c a, a, c, 90, 90, 90
Trigonal One 3-fold axis a, a, c, 90, 90, 120
Hexagonal One 6-fold axis a, a, c, 90, 90, 120
Cubic Four 3-folds along space diagonal a, a, ,a, 90, 90, 90
Chapter 3 -
Crystal Systems Crystal structures are divided into groups according to
unit cell geometry (symmetry).

Chapter 3 -
Chapter 3 - 51
Crystal Systems – Some Definitional information

All periodic unit cells may be described via

these vectors and angles, if and only if
• a, b, and c define axes of a 3D
coordinate system.
• coordinate system is Right-Handed!

But, we can define points, directions and

planes with a “triplet” of numbers in units
of a, b, and c unit cell vectors.

For HCP we need a “quad” of numbers, as

we shall see.

Miller indices- shorthand notation used to

describe the directions in the unit cell
Chapter 3 - 52
 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 - 53
 Point coordinates
To define a point within a unit cell….
Express the coordinates hkl as fractions of unit cell vectors a, b, and c
(so that the axes x, y, and z do not have to be orthogonal).

Point
Coordinates

000

100

111

101

Chapter 3 - 54
 General Rules for Lattice Directions,
Planes & Miller Indices

• Miller indices used to express lattice planes and directions

• x, y, z are the axes (on arbitrarily positioned origin)
• a, b, c are lattice parameters (length of unit cell along a side)
• u, v, w are the Miller indices for planes and directions -
expressed as planes: (hkl) and directions: [hkl]

Conventions for naming • Crystallographic

– There are NO COMMAS between
numbers
direction:
– Negative values are expressed – [123]
with a bar over the number – [100]
• Example: -2 is expressed 2 – … etc.

Chapter 3 - 55
 Miller Indices for Directions
Method

– Draw vector, and find the coordinates

of the head, h1,k1,l1 and the tail
h2,k2,l2.
– subtract coordinates of tail
from coordinates of head
– Remove fractions by
multiplying by smallest
possible factor
– Enclose in square brackets

Chapter 3 - 56
Procedure:
1. Any line (or vector direction) is specified by 2 points.
• The first point is, typically, at the origin (000).
• If not determine the coordinates and note it as tail

2. Determine length of vector projection in each of 3 axes in

units (or fractions) of a, b, and c note this as the head
•X (a), Y(b), Z(c)
110

3. Subtract the coordinates of the tail to the head.

•(head - tail)

4. Multiply or divide by a common factor to reduce the

lengths to the smallest integer values, hkl.

5. Enclose in square brackets: [hkl]: [110] direction.

6. Designate negative numbers by a bar [1 1 0]

• Pronounced “bar 1”, “bar 1”, “zero” direction.

7. “Family” of [110] directions is designated as <110>.

Chapter 3 - 57
Chapter 3 - 58
Chapter 3 - 59
Chapter 3 - 60
 Find the Miller indices for Find the Miller indices for the
the points in the cubic unit directions in the cubic unit cell
cell below: below:

Note: J is on the left face of the cube, H is on the

right face,
K is on the front face and I is on the back face
Chapter 3 - 61
Families of Directions

Chapter 3 - 62
 Note: for some crystal structures, different directions can be equivalent.
e.g. For cubic crystals, the directions are all equivalent by symmetry:

[1 0 0], [ 1 0 0], [0 1 0], [0 1 0], [0 0 1], [0 0 1 ]

Families of crystallographic directions

e.g. <1 0 0>
Angled brackets denote a family of crystallographic directions
Chapter 3 - 63
 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 - 64
 Importance of Miller Indices of Planes in Unit cells

Metals deform on close packed

planes in close packed directions

Lasers are grown by vapor

depositing layer by layer of atoms
on a specific plane

Gems such as rhodochrosite and

diamond grow on planes that
reflect crystal structure

Chapter 3 - 65
Why are planes in a lattice important?

(A) Determining crystal structure

* Diffraction methods measure the distance between parallel lattice planes of
atoms.
• This information is used to determine the lattice parameters in a crystal.
* Diffraction methods also measure the angles between lattice planes.

(B) Plastic deformation

* Plastic deformation in metals occurs by the slip of atoms past each other in the
crystal.
* This slip tends to occur preferentially along specific crystal-dependent planes.

(C) Transport Properties

* In certain materials, atomic structure in some planes causes the transport of
electrons
and/or heat to be particularly rapid in that plane, and relatively slow not in the
plane.

• Example: Graphite: heat conduction is more in sp2-bonded plane.

• Example: YBa2Cu3O7 superconductors: Cu-O planes conduct pairs of electrons

(Cooper pairs) responsible for superconductivity, but perpendicular insulating.
+ Some lattice planes contain only Cu and O Chapter 3 - 66
Auguste Bravais
Lattices
(1811-1863)

• In 1848, Auguste Bravais demonstrated

that in a 3-dimensional system there are
fourteen possible lattices
• A Bravais lattice is an infinite array of
discrete points with identical environment
• seven crystal systems + four lattice
centering types = 14 Bravais lattices
• Lattices are characterized by translation
symmetry

Chapter 3 -
14 Crystal Lattices

Chapter 3 - 68
 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 - 69
 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 - 70