Course

Crystal Structure and Analysis

 Chapter # 3:
Materials Science and Engineering
William D. Callister, David G. Rethwisch
Chapter 3: The Structure of Crystalline Solids

Chapter 3 -
 Introduction
• The fundamental difference between single crystal ,
polycrystalline and amorphous solids is the length scale
over which the atoms are related to one another by
translational symmetry ('periodicity' or 'long-range
order').

Chapter 3 -
 Single Crystalline
• An ideal single crystal has an atomic structure that
repeats periodically across its whole volume.
• Even at infinite length scales, each atom is related to
every other equivalent atom in the structure by
translational symmetry

Chapter 3 -
 Polycrystalline
• A polycrystalline solid or polycrystal is comprised of many individual
grains or crystallites.
• Each grain can be thought of as a single crystal, within which the
atomic structure has long-range order.
• In an isotropic polycrystalline solid, there is no relationship between
neighboring grains. Therefore, on a large enough length scale, there
is no periodicity across a polycrystalline sample.

Chapter 3 -
 Crystallite/Grains
• Crystallites are tiny (usually microscopic) crystals that
are bonded together by boundaries that are highly
irregular, comprising polycrystalline solids.
• Crystallites are also known as grains

Chapter 3 -
 Amorphous

• Amorphous materials, like window glass, have no

long-range order at all, so they have no translational
symmetry.
• The structure of an amorphous solid (and indeed a
liquid) is not truly random - the distances between
atoms in the structure are well defined and similar to
those in the crystal.
• This is why liquids and crystals have similar densities
- both have short-range order that fixes the distances
between atoms, but only crystals have long-range
order
Chapter 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.

Chapter 3 -
 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 -
 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 -
 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 -
 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)

(Courtesy P.M. Anderson)

Chapter 3 -
Chapter 3 -
 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,
Chapter 3 -
Callister & Rethwisch 8e.
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,

Callister & Rethwisch 8e.
(Courtesy P.M. Anderson)
2 atoms/unit cell: 1 center + 8 corners x 1/8
Chapter 3 -
Chapter 3 -
 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 Chapter 3 -
 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.

(Courtesy P.M. Anderson) 4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

Chapter 3 -
Chapter 3 -
 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 3
unit cell 4 p ( 2a/4) atom
3
APF =
3 volume
a
unit cell
Chapter 3 -
 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 -
 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 -
 Theoretical Density, r

Mass of Atoms in Unit Cell

Density =  =
Total Volume of Unit Cell

nA
 =
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 -
 Theoretical Density, r
• 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
= ractual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol Chapter 3 -
 Densities of Material Classes
In general Metals/
Graphite/
Composites/
rmetals > rceramics > rpolymers Alloys
Ceramics/
Semicond
Polymers
fibers
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
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 -
 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 -
 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 -
 Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa
Data from Table 3.3,
-Properties vary with Callister & Rethwisch
8e. (Source of data is
direction: anisotropic. R.W. Hertzberg,
Deformation and
-Example: the modulus Fracture Mechanics of
Engineering Materials,
of elasticity (E) in BCC iron: 3rd ed., John Wiley and
Sons, 1989.)

E (edge) = 125 GPa

• Polycrystals
-Properties may/may not 200 mm Adapted from Fig.
4.14(b), Callister &
vary with direction. Rethwisch 8e.
(Fig. 4.14(b) is courtesy
-If grains are randomly of L.C. Smith and C.
Brady, the National
oriented: isotropic. Bureau of Standards,
Washington, DC [now
(Epoly iron = 210 GPa) the National Institute of
-If grains are textured, Standards and
Technology,
anisotropic. Gaithersburg, MD].)

Chapter 3 -
 Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538ºC
carbon BCC -Fe
diamond, graphite 1394ºC
FCC -Fe
912ºC
BCC -Fe

Chapter 3 -
 Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.

7 crystal systems

14 Bravais lattices

a, b, and c are the lattice constants

Fig. 3.4, Callister & Rethwisch 8e.

Chapter 3 -
UNIT CELL TYPES and THE SEVEN CRYSTAL SYSTEMS

Cubic a = b = c.  =  =  = 90º. c b
Tetragonal a = b  c.  =  =  = 90º.
Orthorhombic a  b  c.  =  =  = 90 º. a
Monoclinic a  b  c.  = = 90º,   90º. Orthorhombic
Triclinic a  b  c..       90º.
Rhombohedral a = b = c.  =  =   90 º.
(or Trigonal)
Hexagonal a = b  c.  =  = 90º,  = 120º.

In general, six parameters are required to define the shape and size of a unit cell,
these being three cell edge lengths (conventionally, defined as a, b, and c),
and three angles (conventionally, defined as , , and ). In the strict mathematical
sense, a, b, and c are vectors since they specify both length and direction.
a is the angle between b and c,  is the angle between a and c,  is the angle
between a and b. The unit cell should be right handed. Check the cell above with
your right hand
When these unit cells are combined with possible “centering” there are
14 different Bravais lattices.

Chapter 3 -
Chapter 3 -
 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 -
 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 -
 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 -
 Crystallographic Directions
Family of directions
• The components for any family of directions is basically
the set of all permutations of the family indices - both
positive and negative.
• The simplest family of directions <100> would have the
following components:

Chapter 3 -
 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 -
 HCP Crystallographic Directions
z
Algorithm
1. Vector repositioned (if necessary) to pass

through origin.
a2 2. Read off projections in terms of unit
cell dimensions a1, a2, a3, or c
- 3. Adjust to smallest integer values
a3
4. Enclose in square brackets, no commas
a2
a1 [uvtw]
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 -
 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 -
 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 -
 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 -
 Crystallographic Planes

Adapted from Fig. 3.10,

Callister & Rethwisch 8e.
Chapter 3 -
Chapter 3 -
 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 -
 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 -
 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
Planar Density = = 2 = 12.1 = 1.2 x 10 19

area a2 4 3 nm 2
m2
R
2D repeat unit 3
Chapter 3 -
 Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell

2a atoms in plane
atoms above plane

ni t
atoms below plane

tu
ea
rep
3
h= a
2D 2
2
æ4 3 ö 16 3 2
area = 2 ah = 3 a = 3 çç
2
R  = R
atoms è 3 ø 3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
area 16 3 2
nm
2
m2
R
2D repeat unit 3
Chapter 3 -
 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 -
 X-Rays to Determine Crystal Structure
• Incoming X-rays diffract from crystal
d planes. et
ec
to

”
r

“1
in -ra
co ys
X
y s reflections must

m
-ra be in phase for
in

”
“2
X
g
a detectable signal

“1
g

”
n l
extra
oi
“2
g Adapted from Fig. 3.20,
distance
q ut q
”
o Callister & Rethwisch 8e.
travelled
by wave “2” spacing
d between
planes

Measurement of X-ray
intensity nl
critical angle, qc, d=
(from 2 sin qc
allows computation of
detector)
planar spacing, d.
q
qc
Chapter 3 -
 Bragg’s law
de
te
c to

”
r

“1
in -ra
s

co ys
y

X
reflections must
ra

m
- be in phase for

”
in “2”
X

“2
a detectable signal

“1
g
g

”
extra
distance g oi
n l Adapted from Fig. 3.20,
travelled q o ut q Callister & Rethwisch
8e.
by wave “2” spacing
d between
planes

A simplistic model to understand what conditions are required for diffraction.

• For parallel planes of atoms, with a space d hkl between the planes, constructive
interference only occurs when Bragg’s law is satisfied.
– In our diffractometers, the X-ray wavelength l is fixed.
– Consequently, a family of planes produces a diffraction peak only at a specific angle q.
– Additionally, the plane normal must be parallel to the diffraction vector
• Plane normal: the direction perpendicular to a plane of atoms
• Diffraction vector: the vector that bisects the angle between the incident and diffracted beam
• The space between diffracting planes of atoms determines peak positions.
• The peak intensity is determined by what atoms are in the diffracting plane.
Chapter 3 -
Diffraction occurs when light is scattered by a periodic array
with long-range order, producing constructive
interference at specific angles.

• The electrons in each atom coherently scatter light.

– We can regard each atom as a coherent point scatterer
– The strength with which an atom scatters light is proportional to the number of electrons around the atom.

• The atoms in a crystal are arranged in a periodic array with long-

range order and thus can produce diffraction.
• The wavelength of X rays are similar to the distance between
atoms in a crystal. Therefore, we use X-ray scattering to study
atomic structure.
• The scattering of X-rays from atoms produces a diffraction
pattern, which contains information about the atomic
arrangement within the crystal
• Amorphous materials like glass do not have a periodic array with long-range order, so they do not produce
a diffraction pattern. Their X-ray scattering pattern features broad, poorly defined amorphous ‘humps’.

Chapter 3 -
 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 a-iron (BCC)

Adapted from Fig. 3.22, Callister 8e.

Chapter 3 -
A single crystal specimen in a Bragg-Brentano diffractometer
would produce only one family of peaks in the diffraction
pattern.

2q

At 20.6 °2q, Bragg’s law The (110) planes would diffract at 29.3 The (200) planes are parallel to the (100)
fulfilled for the (100) planes, °2q; however, they are not properly planes. Therefore, they also diffract for this
producing a diffraction peak. aligned to produce a diffraction peak crystal. Since d200 is ½ d100, they appear at
(the perpendicular to those planes 42 °2q.
does not bisect the incident and
diffracted beams). Only background is
observed. Chapter 3 -
 A polycrystalline sample should contain thousands of
crystallites. Therefore, all possible diffraction peaks should
be observed.

2q 2q 2q

• For every set of planes, there will be a small percentage of crystallites that are properly
oriented to diffract (the plane perpendicular bisects the incident and diffracted beams).
• Basic assumptions of powder diffraction are that for every set of planes there is an equal
number of crystallites that will diffract and that there is a statistically relevant number of
crystallites, not just one or two. Chapter 3 -
 Powder diffraction data consists of a record of
photon intensity versus detector angle 2q.
• Diffraction data can be reduced to a list of peak positions and intensities
– Each dhkl corresponds to a family of atomic planes {hkl}
– individual planes cannot be resolved- this is a limitation of powder diffraction
versus single crystal diffraction
Raw Data Reduced dI list
Position Intensity hkl dhkl (Å) Relative
[°2q] [cts] Intensity
25.2000 372.0000 (%)
25.2400 460.0000
25.2800 576.0000
{012 3.4935 49.8
}
25.3200 752.0000
25.3600 1088.0000 {104 2.5583 85.8
25.4000 1488.0000 }
25.4400 1892.0000 {110} 2.3852 36.1
25.4800 2104.0000
25.5200 1720.0000
{006 2.1701 1.9
}
25.5600 1216.0000
25.6000 732.0000 {113} 2.0903 100.0
25.6400 456.0000
{202 1.9680 1.4
25.6800 380.0000
}
25.7200 328.0000
 You can use XRD to determine
• Phase Composition of a Sample
– Quantitative Phase Analysis: determine the relative amounts of phases
in a mixture by referencing the relative peak intensities
• Unit cell lattice parameters and Bravais lattice symmetry
– Index peak positions
– Lattice parameters can vary, and therefore give you information about,
alloying, doping, solid solutions, strains, etc.
• Residual Strain (macrostrain)
• Crystal Structure
– By Rietveld refinement of the entire diffraction pattern
• Epitaxy/Texture/Orientation
• Crystallite Size and Microstrain
– Indicated by peak broadening
– Other defects (stacking faults, etc.) can be measured by analysis of
peak shapes and peak width
• We have in-situ capabilities, too (evaluate all properties above as a
function of time, temperature, and gas environment)
 Unit Cell Lattice Parameter Refinement

• By accurately measuring peak positions over a long

range of 2theta, you can determine the unit cell lattice
parameters of the phases in your sample
– alloying, substitutional doping, temperature and pressure, etc
can create changes in lattice parameters that you may want to
quantify
– use many peaks over a long range of 2theta so that you can
identify and correct for systematic errors such as specimen
displacement and zero shift
– measure peak positions with a peak search algorithm or profile
fitting
• profile fitting is more accurate but more time consuming
– then numerically refine the lattice parameters
 Calculations using X-ray powder diffraction patterns.

For an orthogonal system (a = b =  = 90°) the relationship between

interplanar spacing (d) and the unit cell parameters is given by the
expression:

This is the expression for an orthorhombic crystal

1 h2 k2 l2
2
 2
 2

d ( h, k , l ) a b c2

For the tetragonal system it reduces to

1 (h 2  k 2 ) l2
2
 2

d ( h,k ,l ) a c2

and, for the cubic system, it further reduces to

1 (h 2  k 2  l 2 )
2

d ( h,k ,l ) a2
 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 -
 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 -