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?
 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.
2
 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.

3
 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

4
 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...

5
Definition of terms:

Unit Cell

• Unit cell is the subdivision of the crystalline lattice

that still retains the overall characteristics of the
entire lattice.
•all the atom positions in the crystal may be
generated by translations of the unit cell integral
distances along each of its edges.
• It defines the crystal structure by virtue of its
geometry and the atom positions within.
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.

Atomic Packing Factor (APF)

 The fraction of space occupied by atoms, assuming

that atoms are hard spheres.
 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)

8
 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
Adapted from Fig. 3.24,
Callister & Rethwisch 8e. 9
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
10
 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 p ( 3a/4 ) 3
3 atom
APF =
3 volume
a
unit cell 11
 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

12
The coordination number for FCC metals, CN = 12,

• the front face atom has 4 corner nearest

neighbor atoms surrounding it,
• 4 face atoms that are in contact from behind
• 4 other equivalent face atoms residing in the
next unit cell to the front.
 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 =
volume
a3
unit cell
14
 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

15
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 16
 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
 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 18
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) p R3 = p .
16 R3 2 32
= 0.74

19
 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 r = 8.94 g/cm3 a = 2R2 ; Vc = (2R 2)3 = 16R32
Req’d: r & compare w/ measured
Sol’n: r= n A .

r= 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

20
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. r = 7.87 g/cm3

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

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

21
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
 Densities
In general
of Material Classes Graphite/
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
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 G raphite
Silicone CFRE *
A ramid 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.
23
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

24
 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.

25
Crystallographic Directions, and Planes

26
 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 edge lengths
, , and  are interaxial angles

14 crystal lattices

Fig. 3.4, Callister 7e.

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
Crystal Systems Crystal structures are divided into groups according to
unit cell geometry (symmetry).
 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
14 Crystal Lattices

31
Crystal Structure of Metals – of
engineering interest
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.
Fig. 3.4, Callister 7e.

Miller indices- shorthand notation used to

describe the directions in the unit cell
33
 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
34
 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

35
 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
direction:
numbers
– Negative values are expressed – [123]
with a bar over the number – [100]
• Example: -2 is expressed 2 – … etc.

36
 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

37
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>.

38
39
40
41
 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
42
Families of Directions

43
 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
44
 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)

45
 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

46
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
47
48
 Miller Indices for PLANES

Method

• If the plane passes through the

origin, select an equivalent plane
or move the origin

• Determine the intersection of the

plane with the axes in terms of a,
b, and c

• Take the reciprocal (1/∞ = 0)

• Convert to smallest integers

(optional)

• Enclose by parentheses

49
Procedure

Given Plane >Determine indices

1. Choose origin O in unit cell
2. Find intercepts from O to a intercept; from O to b int; from O to c int
A plane which is parallel to any one of the co-ordinate axes has an
intercept of infinity (). Therefore the Miller index for that axis is zero;
i.e. for an intercept at infinity, the corresponding index is zero.
3. Take reciprocals of intercept position
4. Clean up a) Reduce multiples
b) Eliminate fractions
c) Put – above negative integer in indices
d) Place parentheses
It is only the ratio of the indices which is important in this notation. The
(6 2 2) planes are the same as (3 1 1) planes.

Choose Origin
Unit cell a b c
2. Intercept
3a. Reciprocal
3b. Reciprocal value
4. Miller Indices 50
 Crystallographic Planes
z
Choose Origin 0 0 0
c
Unit cell a b c
2. Intercept 1 1 
3a. Reciprocal 1/1 1/1 1/
y
3b. Reciprocal value 1 1 0
a b
4. Miller Indices (110)
x
z
Choose Origin 0 0 0
c
Unit cell a b c
2. Intercept 1/2  

3a. Reciprocal 1/ 1/ 1/ y

1/2 a b
3b. Reciprocal value 2 0 0
x
4. Miller Indices (100)
51
Choose Origin
Unit cell a b c
2. Intercept
3a. Reciprocal
3b. Reciprocal value
4. Miller Indices

52
Choose Origin
Unit cell a b c
2. Intercept
3a. Reciprocal
3b. Reciprocal value
4. Miller Indices

53
Choose Origin
Unit cell a b c
2. Intercept
3a. Reciprocal
3b. Reciprocal value
4. Miller Indices

54
Choose Origin
Unit cell a b c
2. Intercept
3a. Reciprocal
3b. Reciprocal value
4. Miller Indices

55
Choose Origin
Unit cell a b c
2. Intercept
3a. Reciprocal
3b. Reciprocal value
4. Miller Indices

56
Choose Origin
Unit cell a b c
2. Intercept
3a. Reciprocal
3b. Reciprocal value
4. Miller Indices

57
Summary

58
59
60
61
 Crystallographic Planes

Adapted from Fig. 3.10,

Callister & Rethwisch 8e.
62
Procedure

Given Indices >Draw plane

1. Select origin O in unit cell
2. Take reciprocals of indices to get 1/h, 1/k, 1/l which will be the
intercept
3. Mark intercepts along x, y, and z axes
4. Draw plane by connecting intercepts

Choose Origin
2a. Reciprocal
2b. Reciprocal Value
Unit cell a b c
Mark intercepts
Draw

63
Example (100)

1. Select origin O in unit cell

2. Take reciprocals of indices to get 1/h, 1/k, 1/l which will be the
intercept
3. Mark intercepts along x, y, and z axes
4. Draw plane by connecting intercepts

Choose Origin
2a. Reciprocal
2b. Reciprocal Value
Unit cell a b c
Mark intercepts
Draw

64
Family of Planes {hkl}
Ex: {100} = (100), (010), (001), (100), (010), (001)

65
Find the Miller indices of the given planes

1 2 3 4

5 6 7 8

Draw the plane of the following miller indices of planes

(2 2 1), (1 1 2) (1 0 2) (1 2 1) (2 0 2) (0 2 1)
9 10 11 12 13 14

66
67
 HCP Crystallographic Directions
• Hexagonal Crystals
– 4 parameter Miller-Bravais lattice coordinates are
related to the direction indices (i.e., u'v'w') as follows.

[ 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.

68
 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
69
Computing HCP Miller- Bravais Directional Indices (an
alternative way):
We confine ourselves to the bravais
parallelopiped in the hexagon: a1-
z a2-Z and determine: (u’,v’w’)

u= 1
Here:
 3
 [1
 1 0] - so now apply the
2u '  v ' = 1
3
2 1  1 = 1
3
1

v= 1models
 3
  to create M-B Indices
2v ' u ' = 1
3
2 1  1 = 1
3
1


t =  u  v  =  1
3
 1
3  =  2 3  2
w = w' = 0
a2
M-B Indices: [11 20]

a3
-
a1
71
72
Origin
axes U’ V’ W’
intercept
U= 1/3(2u’-v’)
V=1/3(2v’-u’)
W=w’
T= -(u+v)
4 index notation
Miller Bravais Indices

73
 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.

74
75
76
77
78
Find the 4 Miller Bravais indices of Find the 4 Miller Bravais indices of the
points A C E F. plane below

79
80
 Linear and Planar Atomic Densities
Linear Density:
Directional equivalency is related to the atomic linear density in the
sense that equivalent directions have identical linear densities.
The direction vector is positioned so as to pass through atom centers.
The fraction of line length intersected by these atoms is equal to the
linear density.

Planar Density:
Crystallographic planes that are equivalent have the same atomic planar
density. The plane of interest is positioned so as to pass through atom
centers.
Planar density is the fraction of total crystallographic plane area that is
occupied by atoms.

Linear and planar densities are one- and two-dimensional

analogs of the atomic packing factor.
Determining Angles Between Crystallographic
Direction:

 
u1u2  v1v2  w1w2
 = Cos 1  
 2 
  2 2
 
u1  v1  w1  u2  v2  w2 
2 2 2
 

Where ui’s , vi’s & wi’s are the “Miller Indices” of the
directions in question

– also (for information) If a direction has the same Miller

Indices as a plane, it is NORMAL to that plane
Linear Density

83
 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.

84
Linear Packing Density

85
Planar Density

86
 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
87
 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
88
 Planar Density of (111) Iron
Solution (cont): (111) plane 1/2 atom centered on plane/ unit cell

2a atoms in plane
atoms above plane
atoms below plane

3
h= a
2

Area 2D Unit: ½ hb = ½*[(3/2)a][(2)a]=1/2(3)a2=8R2/(3)

atoms
2D repeat unit 3*1/6
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
2
nm m2
area 8R 2
2D repeat unit 3
Planar Packing Density

90
Derive the linear density expression for BCC [110] and
FCC [111] directions in terms of the atomic radius R.

Derive the planar density expression for BCC (100) and

FCC (100)

91
 Chapter 3.2 Crystalline and Noncrystalline
Materials

Single Crystals
Polycrystalline Materials
Anisotropy
Noncrystalline Solids

92
 Crystals as Building Blocks
• Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives
Fig. 8.33(c), Callister 7e.
(Courtesy Martin Deakins, (Fig. 8.33(c) courtesy
GE Superabrasives, of Pratt and 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)
 Single crystal
- The crystal with a periodic and repeated arrangement of
atoms is perfect or extends throughout the entirety of
the specimen without interruption is referred to as single
crystal
- Exist in nature or can be produced artificially
- Ordinarily difficult to grow because the environment
must be carefully controlled.

94
 Polycrystalline Materials
- Solids that are composed of a collection of many
small crystals or grains are termed polycrystalline
materials.

95
 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 typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Anisotropic – a material whose properties
depend on the crystallographic direction along
which the property is measured.

Isotropic – a material whose properties are

independent on the direction of measurement

97
Effects of Anisotropy:
 Single vs Polycrystals
• Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
• 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
Source of data is R.W.
Hertzberg, Deformation
and Fracture Mechanics
of Engineering
Materials, 3rd ed., John
Wiley and Sons, 1989.
E (edge) = 125 GPa
200 mm
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].
 Noncrystalline Solid

Noncrystalline solids lack a

systematic and regular
arrangement of atoms over crystalline SiO2
Adapted from Fig. 3.23(a),
relatively large atomic Callister & Rethwisch 8e.

distances. Si Oxygen
Amorphous – meaning
literally without form

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

100
 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

101
 4
SiO4
 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.
103
104
105
106
 X-Ray Diffraction:

• Measure the crystal structure of engineering

materials.

• Determine the structure of a new material

• It is used as a source of chemical identification.

107
108
109
110
 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. 3.19,
 
distance
Callister 7e.
traveled
by wave “2” spacing
d between
planes
Measurement of
critical angle, c,
allows computation of X-ray
n
planar spacing, d. intensity d=
(from 2 sin c
For Cubic Crystals: detector)
d hkl =
a 
h2  k 2  l 2 c
h, k, l are Miller Indices
Figure 3.34 (a) An x-ray diffractometer. (Courtesy of Scintag,
Inc.) (b) A schematic of the experiment.
 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 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.20, Callister 5e.
Diffraction in Cubic Crystals:
 Planes in Lattices and Bragg’s Law
We are interested in the planes in a crystal lattice in the context of X-ray diffraction
because of Bragg’s Law:
n = 2 d sin()
Where:
n is an integer

 is the wavelength of the X-rays

d is distance between adjacent

planes in the lattice

 is the incident angle of the X-ray

beam

Bragg’s law tells us the conditions that must be met for the reflected X-ray waves to be in phase
with each other (constructive interference). If these conditions are not met, destructive
interference reduces the reflected intensity to zero!

W.H.Bragg and son W.L.Bragg were awarded the Nobel prize in 1915.
 Simple derivation of Bragg’s Law
Bragg’s Law can be derived using simple geometry by considering the distances
traveled by two parallel X-rays reflecting from adjacent planes. The X-ray hitting the
lower plane must travel the extra distance AB and BC. To remain in phase with the
first X-ray, this distance must be a multiple of the wavelength thus:
n = AB+BC = 2AB
(since the two triangles are identical)

The distance AB can be expressed in terms of

the interplanar spacing (d) and incident angle ()
because d is the hypotenuse of right triangle zAB
shown at right. Remember sin =
opposite/hypotenuse

sin() = AB/d thus AB = d sin()

Therefore:
n = 2 d sin()
Note: d and sin() are inversely proportional
(reciprocal). This means that smaller values
of d diffract at higher angles – this is the
importance of “high angle” data!
 Diffraction of X-rays
You may wonder why to X-rays reflect in this way and what is causing them
to “reflect” in the first place. The actual interaction is between the X-rays and
the ELECTRONS in the crystal and it is a type of elastic scattering. The
oscillating electric field of the X-rays causes the charged particles in the
atom to oscillate at the same frequency. Emission of a photon at that
frequency (elastic) returns the particles in the atom to a more stable state.
The emitted photon can be in any direction and the intensity of the scattering
is given by the equation:

I(2) = Io [(n e4)/(2 r2 m2 c4)] [(1 + cos2(2))/2]

I(2) = observed intensity

Io = incident intensity
n = number of scattering sources
r = distance of detector from scattering source
m = mass of scattering source
c = speed of light, e = electron charge, [(1 + cos2(2))/2] is a polarization factor

Note that the mass of the scattering particle (m) is in the denominator – this
means that the scattering that we see is attributable only to the electrons
(which have masses almost 2000 times less than that of a proton).
 Laue’s interpretation

Max von Laue derived a different set of equations describing the “in phase” diffraction
of X-rays by a line of scattering objects (note that the n in the diagram below is the
integer corresponding to the integer n in the Bragg equation). Each line of objects
generates cones of “in phase” scattering that follow the equations:

a(cos Y1 – cos j1) = h (for a line in the a direction)

b(cos Y2 – cos j2) = k (for a line in the b direction)
c(cos Y3 – cos j3) = l (for a line in the c direction)

Where Y is the angle between the incident beam and the

line and j is the angle between the cone and the line of
scatterers. In three dimensions, a reflection will only be
observed at the intersection of the cones in all three
directions (all three equations are satisfied).

With a little geometry (see Ladd and Palmer 3.4.3), it can

be shown that this treatment is equivalent to Bragg’s law.
 Cesium chloride (CsCl) unit cell showing (a) ion positions and the two ions per
lattice point and (b) full-size ions. Note that the Cs+−Cl− pair associated with a
given lattice point is not a molecule because the ionic bonding is nondirectional
and because a given Cs+ is equally bonded to eight adjacent Cl−, and vice versa.
[Part (b) courtesy of Accelrys, Inc.]
 Sodium chloride (NaCl)
structure showing (a) ion
positions in a unit cell, (b)
full-size ions, and (c) many
adjacent unit cells. [Parts
(b) and (c) courtesy of
Accelrys, Inc.]
Fluorite (CaF2) unit cell showing (a) ion positions and (b) full-size ions. [Part (b)
courtesy of Accelrys, Inc.]
 4
SiO4
 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.

123
 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.

124