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 orientation?

1
•The properties of some materials are directly related to
their crystal structures:

Pure and undeformed magnesium, having one crystal structure, is much

more brittle (i.e., fracture at lower degrees of deformation) than are pure
and undeformed metals such as gold and silver that have yet another
crystal structure.

•Significant property differences exist between

crystalline and noncrystalline materials having the same
composition, as well:
Noncrystalline ceramics and polymers normally are optically transparent; the
same materials in crystalline (or semicrystalline) form tend to be opaque or, at
best, translucent.

2
Definition:
Crystalline and Noncrystalline (Amorphous)

•Solid materials may be classified according to the regularity with which atoms 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;

•Upon solidification, the atoms will position themselves in a repetitive three-

dimensional pattern, in which each atom is bonded to its nearest-neighbor atoms.

• All metals, many ceramic materials, and certain polymers form crystalline
structures under normal solidification conditions.

•For those that do not crystallize, this long-range atomic order is absent: these are
called as noncrystalline or amorphous materials.

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" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.

4
 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.
5
There is an extremely large number of different crystal
structures all having long range atomic order; these vary
from relatively simple structures for metals to exceedingly
complex ones, as displayed by some of the ceramic and
polymeric materials.

When describing crystalline

structures, atoms (or ions) are
thought of as being solid spheres
having well-defined diameters.
This is termed as “atomic hard
sphere model” in which spheres
representing atoms touch one
another.
All the atoms are
identical
6
 Lattice: A three dimentional array of
points coinciding with atom positions

•In describing crystal structures, it is

often convenient to subdivide the
structure into small repeat entities
called unit cells.

•Unit cells for most crystal structures are

prisms having three sets of parallel
faces.

-The unit cell is the basic structural unit or building block

of the crystal structure
-Defines the crystal structure by virtue of its geometry and
the atom positions within.
7
Lattice parameter relationships and
figures showing unit cell geometries
for the seven crystal system:

•Simple Cubic Structure (SC)

•Body Centered Cubic Structure (BCC)
•Face Centered Cubic Structure (FCC)
•Hexagonal Close-Packed Structure
(HCP)

8
 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

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...

10
 Simple Cubic Structure (SC)
• Rare due to low packing density
• Only Po (Polonium) has this structure.
• Close-packed directions are cube edges.
• Coordination # = 6
(Number of nearest neighbors)

1
2
4
3
5

11
Simple Cubic Structure (SC)
 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 p (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 = 1 atom/unit cell

13
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 ()
• Coordination # = 8

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

14
Body Centered Cubic Structure (BCC)
Body Centered Cubic Structure (BCC)
 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a R

2R a
R

2a

Close-packed directions:
R length = 4R = 3 a
a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell 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, Ni, Ag

• Coordination # = 12

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

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Face Centered Cubic Structure (FCC)
 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
atoms volume
4
unit cell 4 p ( 2a/4) 3
3 atom
APF =
volume
a3
unit cell
20
 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

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• 3D Projection of FCC Unit Cell: Close-packed (111) planes:

22
CUBIC CRYSTAL STRUCTURES
 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

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 24
Hexagonal Close-Packed Structure
(HCP)

25
 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

26
 Theoretical Density, r
• Ex: Cr (Chromium) (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
a a = 4R/ 3 = 0.2887 nm

atoms
g
unit cell 2 52.00
mol
r= rtheoretical = 7.18 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol 27
 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

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 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

29
 Crystal Systems

•When dealing with crystalline materials, it often becomes

necessary to specify a particular point within a unit cell, a
crystallographic direction, or some crystallographic plane
of atoms.

•Labeling conventions have been established in which

three numbers or indices are used to designate point
locations, directions, and planes.

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 Point Coordinates
•The position of any point located within a unit cell may be
specified in terms of its coordinates as fractional multiples of
the unit cell edge lengths.
•We have chosen not to separate these coordinates by
commas or any other punctuation marks.

Point Coordinates: qrs

The “q” coordinate (which is a fraction)

corresponds to the distance “qa” along the x
axis, where “a” is the unit cell edge length.
The respective r and s coordinates for the y
and z axes are determined similarly.

31
EXAMPLE 1: Fractional multiples of the unit
cell edge lengths

32
EXAMPLE 2: Specify point coordinates for all atom positions for a
BCC unit cell.
z
111
c

000
y
a b
x

33
 Crystallographic Directions
•A crystallographic direction is defined as a line
between two points, or a vector.
1. A vector of convenient length is positioned such that it passes through the
origin of the coordinate system.
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 values.
4. The three indices, not separated by commas, are enclosed in square
brackets, thus: [uvw]. The u, v, and w integers correspond to the reduced
projections along the x, y, and z axes, respectively.

34
 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

35
EXAMPLE: Determine the indices for the direction shown in the
accompanying figure:

36
EXAMPLE: Draw a [ 110] direction within a cubic unit cell:

37
Families of directions:
•For some crystal structures, several nonparallel directions with
different indices are actually equivalent: The spacing of atoms
along each direction is the same.
•For example, in cubic crystals, all the directions represented by
the following indices are equivalent:

[100], [100], [010], [ 010], [001], and [001]

•As a convenience, equivalent directions are grouped together

into a family, which are enclosed in “angle brackets”:

•Families of directions <100>

•Directions in cubic crystals having the same indices without
regard to order or sign, for example, [123] and [213], are
equivalent. However, this is not true for other crystal systems.
38
 Linear Density
•Linear density (LD) is defined as the number of atoms per unit
length whose centers lie on the direction vector for a specific
crystallographic direction;

•Equivalent directions have identical linear densities.

39
 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
2
LD = = 3.5 nm-1 2 atoms

length 2a 40
EXAMPLE: Determine the LD on the directions shown in below BCC unit cell.

[111]
[110]

[121] 1 atom
[110]

[111] [121]

2 atoms 1/2 atoms

41
 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
42
 Crystallographic Planes
•In all but the hexagonal crystal system, crystallographic
planes are specified by three Miller indices as (hkl).
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.

43
 Crystallographic Planes
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).

44
 Crystallographic Planes
•Any two planes parallel to each other are equivalent
and have identical indices:

45
 Crystallographic Planes
• Miller Indices: Reciprocals of the (three)
axial intercepts for a plane, cleared of
fractions & common multiples.

• 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)

46
 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 (200) a b
x
47
 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)

48
 Crystallographic Planes
Example: Determine the Miller indices for the plane shown in below figure.

Since the plane passes through the selected origin O, a

new origin must be chosen at the corner of an adjacent
unit cell, taken as O’

49
 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.

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 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 51

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

52
 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

53
VMSE: Crystallographic Planes Exercises

Additional practice on indexing crystallographic planes

54
 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.

55
 Planar Density of (100) Iron
Solution: At T < 912ºC iron has the BCC structure.
z a

(100) 1/4 1/4

1
a

(100) 1/4 1/4

y
1 1 4 3
a= R
x 3
Radius of iron R = 0.1241 nm
atoms
2D repeat unit 4x1/4 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
56
 Planar Density of (111) Iron
Solution (cont): (111) plane:
z

1 •
(111) 1/6

1/6 1/6
• y
1 • 1
x 4 3
atoms a= R
3
2D repeat unit 3x1/6
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
2
nm m2
area
2D repeat unit
57
 Polymorphism
• Two or more distinct crystal structures for the same material: Some metals,
as well as nonmetals, may have more than one crystal structure: Polymorphism
(allotropy/polymorphism)

iron system
titanium
, -Ti liquid
1538ºC
carbon BCC -Fe
diamond, graphite 1394ºC
(Graphite is the stable polymorph at FCC -Fe
ambient conditions, whereas diamond is
formed at extremely high pressures)
912ºC
BCC -Fe

58
 Polymorphism

Temperature C
Example:
Liquid
Iron 1530
BCC Fe
1400
FCC Fe
910

BCC Fe

Time
 Tin (Its Allotropic Transformation) (Sn)

•White tin, having a body-centered

tetragonal crystal structure at room
temperature, transforms, at 13.2 Co, to
gray tin, which has a crystal structure
similar to diamond.

The rate at which this change takes place is extremely slow; however, the lower the temperature the faster
the rate. Accompanying this white tin-to-gray tin transformation is an increase in volume (27 percent), and,
accordingly, a decrease in density (from 7.30 g/cm3 to 5.77 g/cm3). Consequently, this volume expansion
results in the disintegration of the white tin metal into a coarse powder of the gray allotrope. For normal
subambient temperatures, there is no need to worry about this disintegration process for tin products, due
to the very slow rate at which the transformation occurs.

60
Crystalline and Noncrystalline Materials
•Single Crystals:
• For a crystalline solid, when the periodic and
repeated arrangement of atoms is perfect or extends
throughout the entirety of the specimen without interruption,
the result is a single crystal.
• All unit cells interlock in the same way and have the
same orientation.
• Within the past few years, single crystals have
become extremely important in many of our modern
technologies, in particular electronic microcircuits, which
employ single crystals of silicon and other semiconductors.

61
Gallium, a metal that easily Fossile shell with calsite
forms single crystals. crystals.

Garnet (lal taşı)

single crystal.

62
 •Polycrystalline Materials:
•Most crystalline solids are composed of a collection of many small
crystals or grains; such materials are termed polycrystalline.

•Initially, small crystals or nuclei form at various positions. These have

random crystallographic orientations, as indicated by the square grids.

•Small crystals or nuclei

form at various positions.

•random crystallographic
orientations.
LIQUID

63
•The small grains grow by the successive addition from the surrounding
liquid of atoms to the structure of each.
•Adjacent grains touch each other as the solidification process approaches
completion.

Grains

Grain
Boundary

•The crystallographic orientation varies from grain to grain.

• There exists some atomic mismatch within the region where two grains
meet: Grain Boundary.

64
65
66
Crystals as Building Blocks:
• Properties of crystalline materials
often related to crystal structure.
-- Ex: Quartz fractures more easily
along some crystal planes than
others.
-- The elastic modulus, the electrical conductivity, and the index of
refraction may have different values in the [100] and [111]
directions. This directionality of properties is termed anisotropy,
and it is associated with the variance of atomic or ionic spacing
with crystallographic direction.

-- Materials in which measured properties are independent of the

direction of measurement are isotropic.

67
 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.

Preferential crystallographic orientation 68

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).
69
 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.

70
 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).

71