Materials and Metallurgy (ME-209)

TJ TJ
Week
TJ
5 TJ TJ

TJ TJ TJ TJ TJ
The Structure of Crystalline Solids
TJ TJ TJ TJ

TJ TJ TJ TJ TJ
Dr. Tariq Jamil
TJ TJ TJ TJ TJ

E-mail: tariqjamil@neduet.edu.pk
TJ TJ TJ TJ
Office: DICE Energy Lab, MED, NEDUET

1
 Materials and Metallurgy (ME-209)
(According to Course Outline)
TJ TJ TJ TJ TJ

Crystallography: Types of crystal structures, atomic packing factor, Miller indices of

TJ
crystallographic planes TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

2
 Books / Resource Material
TJ TJ TJ TJ TJ

• Text book: “Materials Science and Engineering: An Introduction” by

David G. Rethwisch, 9th Edition
TJ William D. Callister and TJ TJ TJ TJ
• Chapter # 3

TJ TJ TJ TJ
• Reference book: Principles of Material Sciences & Engineering by
William F. Smith, rd
TJ TJ3 Edition TJ TJ TJ

• Online resources
TJ TJ TJ TJ TJ
• Lectures and resource material on Google classroom
• http://wordpress.engineering.iastate.edu/polycomp/files/2012/06/c
h03b.pdf
TJ TJ TJ TJ
• Check YouTube and Wikipedia for further information

3
 Outline
TJ TJ TJ TJ TJ

• How do atoms assemble into solid structures?

TJ TJ TJ TJ TJ

• How does the density of a material depend on its structure?

TJ TJ TJ TJ

TJ • When do material
TJ properties vary
TJwith the sample (i.e.,
TJ part) orientation? TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

4
 Energy and Packing
TJ • Non
TJ dense, random TJ
packing Energy
TJ TJ

typical neighbor
TJ TJ TJ TJ
bond length TJ

typical neighbor r
TJ TJ bond energy TJ TJ

TJ TJ TJ TJ TJ
• Dense, ordered packing Energy

typical neighbor
TJ TJ TJ bond lengthTJ TJ

TJ TJ typical neighbor TJ rTJ

bond energy

Dense, ordered packed structures tend to have

lower energies. 5
TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

6
 Materials and Packing
TJ TJ TJ TJ TJ
Crystalline materials...
• atoms pack in periodic, 3D arrays
TJ TJ TJ TJ TJ
• typical of: -metals
-many ceramics
TJ TJ TJ TJ
-some polymers crystalline SiO2
Adapted from Fig. 3.23(a),
TJ TJ TJ CallisterTJ
& Rethwisch 8e. TJ
Si Oxygen
TJ Noncrystalline
TJ materials... TJ TJ TJ
• atoms have no periodic packing
TJ
• occurs for: -complex
TJ
structures TJ TJ
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e. 7
 Metallic Crystal Structures
TJ TJ TJ TJ TJ
• How can we stack metal atoms to minimize
TJ empty space?
TJ TJ TJ TJ
2-dimensions
TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ vs.TJ TJ TJ

TJ TJ TJ TJ

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

8
 Metallic Crystal Structures
TJ TJ TJ TJ TJ

• Tend to be densely packed.

TJ TJ TJ TJ TJ
• Reasons for dense packing:
- Typically, only one element is present, so all atomic
TJ TJ
radii are the same. TJ TJ

TJ - Metallic
TJ bonding is not directional.
TJ TJ TJ
- Nearest neighbor distances tend to be small in
order to lower bond energy.
TJ TJ
- Electron cloud TJ each other
shields cores from TJ TJ

• Have the simplest crystal structures.

TJ TJ TJ TJ
We will examine three such structures...

9
 Simple Cubic Structure (SC)
TJ TJ TJ TJ TJ
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.
TJ TJ TJ TJ TJ
• Coordination # = 6
TJ TJ (#TJnearest neighbors) TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

Click once on image to start animation

(Courtesy P.M. Anderson)

10
 Atomic Packing Factor (APF)
TJ TJ VolumeTJof atoms in unit cell*TJ TJ
APF =
Volume of unit cell
TJ TJ TJ TJ TJ
*assume hard spheres
TJ • APF for a simple
TJcubic structure = 0.52
TJ TJ

TJ TJ TJ TJ volume TJ
atoms atom
a 4
TJ TJ
unit cell
TJ 1  (0.5a) 3TJ TJ
3
R=0.5a APF =
TJ TJ TJ a3 volume TJ
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.24,
11
Callister & Rethwisch 8e.
 Body Centered Cubic Structure (BCC)
TJ TJ TJ TJ TJ
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
TJ differently only
TJ for ease of viewing. TJ TJ TJ
ex: Cr, W, Fe (), Tantalum, Molybdenum
TJ TJ • TJ
Coordination # = 8 TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ
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
12
 Atomic Packing Factor: BCC
TJ • TJAPF for a body-centered
TJ cubic structureTJ
= 0.68 TJ

3a
TJ TJ TJ TJ TJ
a
TJ TJ TJ TJ
2a
TJ TJ TJ TJ TJ
Close-packed directions:
R
TJ length = 4R = 3 TJ
a
Adapted from
TJ Fig. 3.2(a), Callister & TJ
Rethwisch 8e.
a TJ

atoms volume
4
TJ
unit cell
TJ
2  ( 3a/4) 3 TJ TJ
3 atom
APF =
volume
a3
13
unit cell
 Face Centered Cubic Structure (FCC)
TJ TJ TJ TJ TJ
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
TJ TJ for ease of viewing. TJ
differently only TJ TJ

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

TJ TJ • Coordination
TJ # = 12 TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

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
14
 Atomic Packing Factor: FCC
TJ • APF
TJ for a face-centered
TJ cubic structure = 0.74
TJ TJ
maximum achievable APF
TJ TJ TJ
Close-packed directions:TJ TJ

length = 4R = 2 a
TJ 2a TJ TJ TJ
Unit cell contains:
TJ TJ TJ TJ TJ
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
TJ a TJ TJ TJ TJ
Adapted from
Fig. 3.1(a),
Callister & atoms volume
Rethwisch 8e. 4
TJ unitTJcell 4  ( 2a/4)
TJ 3 TJ
3 atom
APF =
3 volume
a
unit cell 15
 Stacking Sequence
TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

16
 FCC Stacking Sequence
TJ • ABCABC...
TJ Stacking Sequence
TJ TJ TJ
• 2D Projection
TJ TJ B B TJ TJ TJ
C
A
A sites B B B
TJ TJ C C TJ TJ
B sites B B
TJ TJ TJ TJ TJ
C sites
TJ TJ TJ TJ TJ
A
• FCC Unit Cell B
TJ TJ C TJ TJ

17
 Hexagonal Close-Packed Structure
(HCP)
TJ TJ TJ TJ TJ
• ABAB... Stacking Sequence
TJ • 3D Projection
TJ •TJ2D Projection TJ TJ

TJ ATJsites TJ Top layer TJ

c
TJ TJ B sites TJ Middle
TJ layer TJ

A sites Bottom layer

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

TJ • Coordination # =TJ12 6 atoms/unit

TJ cell TJ

• APF = 0.74 ex: Cd, Mg, Ti, Zn

• c/a = 1.633 18
TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

19
 Theoretical Density, 
TJ TJ TJ TJ TJ
Mass of Atoms in Unit Cell
Density =  =
TJ TJ Total Volume
TJ of Unit Cell TJ TJ

nA
 =
TJ TJ VC NA TJ TJ

TJ TJ TJ TJ TJ

where n = number of atoms/unit cell

TJ TJ
A = atomic weightTJ TJ TJ

VC = Volume of unit cell = a3 for cubic

TJ NA =TJAvogadro’s numberTJ TJ
= 6.022 x 1023 atoms/mol

20
 Theoretical Density, 
TJ TJ TJ TJ TJ

• Ex: Cr (BCC)
TJ TJ ATJ= 52.00 g/mol TJ TJ

R = 0.125 nm
TJ TJ TJ TJ
n = 2 atoms/unit cell
TJ TJ R TJ TJ TJ
Adapted from
a a = 4R/ 3 = 0.2887 nm
Fig. 3.2(a), Callister &
Rethwisch 8e.
TJ TJ TJ TJ TJ
atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm 3
TJ TJ mol TJ TJ
= actual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
21
unit cell mol
 Densities of Material Classes Metals/
Graphite/
Ceramics/ Polymers
Composites/
Alloys fibers
TJ TJ TJ TJ Semicond TJ
In general metals > ceramics > polymers 30
Based on data in Table B1, Callister
20 Platinum *GFRE, CFRE, & AFRE are Glass,
Gold, W
TJ Why? TJ TJ Tantalum Carbon, & Aramid Fiber-Reinforced
TJ
Epoxy composites (values based on TJ
Metals have... 10 Silver, Mo
60% volume fraction of aligned fibers
in an epoxy matrix).
• close-packing Cu,Ni
Steels
Tin, Zinc
TJ TJ
(metallic bonding) TJ Zirconia TJ

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

Composites have... 0.3

Data from Table B.1, Callister & Rethwisch, 8e.
• intermediate values
22
 Crystals as Building Blocks
TJ TJ TJ
• Some engineering applications require singleTJcrystals: TJ

-- diamond single -- turbine blades

TJ crystals TJ
for abrasives TJ Fig. 8.33(c), Callister & TJ TJ
Rethwisch 8e. (Fig. 8.33(c)
(Courtesy Martin Deakins,
courtesy of Pratt and
GE Superabrasives,
Whitney).
Worthington, OH. Used with
TJ permission.) TJ TJ TJ

TJ TJ TJ TJ TJ
• Properties of crystalline materials
often related to crystal structure.
TJ TJ TJ TJ TJ
-- Ex: Quartz fractures more easily
along some crystal planes than
TJ others. TJ TJ TJ

(Courtesy P.M. Anderson)

23
 Polycrystals
Anisotropic
• Most engineering materials are polycrystals.
TJ TJ TJ TJ TJ

TJ TJ TJ TJ
Adapted from Fig. K, TJ
color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
TJ TJ TJ Teledyne WahTJ Chang
Albany)

TJ TJ 1 mm TJ TJ TJ

TJ TJ TJ TJIsotropic TJ
• Nb-Hf-W plate with an electron beam weld.
• Each "grain" is a single crystal.
TJ • If grains areTJrandomly oriented, TJ TJ
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). 24
 Single vs Polycrystals
TJ TJ TJ TJ TJ
• Single Crystals E (diagonal) = 273 Gpa @ [111]
-Properties vary with E (edge) = 125 Gpa @ <100>
TJ TJ TJ TJ TJ
direction: anisotropic.
-Example: the modulus
TJ of elasticity (E) TJ
in BCC iron: TJ TJ

TJ TJ TJ TJ TJ
• Polycrystals
-Properties 200 m
TJ may/may not
Adapted from Fig.
TJ TJ TJCallister &
4.14(b), TJ
vary with direction. Rethwisch 8e.
(Fig. 4.14(b) is courtesy
-If grains are randomly of L.C. Smith and C.
Brady, the National
TJ TJ
oriented: isotropic. TJ Bureau of Standards,
TJ
Washington, DC [now
(Epoly iron = 210 GPa) the National Institute of
Standards and
-If grains are textured, Technology,
anisotropic. Gaithersburg, MD].)
25
 Polymorphism
TJ • Two
TJ or more distinct crystal
TJ structures for the
TJ same TJ
material (allotropy/polymorphism)
TJ TJ TJ iron system TJ TJ
titanium
liquid
TJ
, -Ti TJ TJ TJ
1538ºC
TJ TJ TJ BCC -Fe
TJ TJ
carbon
diamond, graphite 1394ºC
TJ TJ TJ
FCC -Fe TJ TJ

912ºC
TJ TJ TJ TJ
BCC -Fe

26
 Crystal Systems
TJ TJ TJ TJ TJ
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
TJ TJ TJ TJ TJ

TJ TJ 7 crystal
TJ systems TJ

TJ TJ TJ TJ TJ

14 crystal lattices
TJ TJ TJ TJ TJ

TJ TJ TJ TJ
a, b, and c are the lattice constants

Fig. 3.4, Callister & Rethwisch 8e.

27
 Crystal Systems
TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

28
 Point Coordinates
z
TJ TJ 111 TJ Point coordinates for
TJ unit cell center are
TJ
c a/2, b/2, c/2 ½½½
TJ TJ TJ TJ TJ

000
y
TJ a bTJ Point coordinates
TJ for unit cell corner
TJ are
111
TJ x TJ TJ TJ TJ

•
TJ z TJ 2c TJ TJ TJ
• Translation: integer multiple of lattice
TJ TJ → identical positionTJin
constants TJ
• • another unit cell
b y
29
b
 Crystallographic Directions
TJ
z
TJ
pt. 2
TJExample 2: TJ TJ
head
pt. 1 x1 = a, y1 = b/2, z1 = 0
TJ TJ 2 = -a, y2 = b,
pt. 2 xTJ z2 = cTJ TJ

TJ y
TJ TJ TJ

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

TJ Multiplying
TJ by 2 to eliminate the
TJ fraction TJ TJ

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

30
 Crystallographic Directions
TJ
z
TJ
Algorithm
TJ TJ TJ
1. Vector repositioned (if necessary) to pass
through origin.
TJ TJ 2. Read off TJ
projections in terms of TJ TJ
unit cell dimensions a, b, and c
y 3. Adjust to smallest integer values
TJ TJ TJ TJ
4. Enclose in square brackets, no commas
TJ
x TJ TJ [uvw] TJ TJ

TJ
ex: 1, 0, ½ TJ=> 2, 0, 1 => [ 201
TJ
] TJ TJ

TJ
-1, 1, 1 => [ 111
TJ
] where overbarTJ
represents a TJ
negative index

Multiple directions can be expressed as a family using V-Bracket <uvw> 31

 Examples of Crystallographic Directions
TJ TJ TJ TJ TJ
y

TJ TJ TJ TJ TJ

TJ TJ x TJ TJ

TJ TJ z TJ TJ TJ

TJ TJ TJ TJ y TJ

TJ TJ TJ TJ x
z

32
 Families of Direction
TJ TJ TJ TJ TJ

• Crystallographically equivalent direction are represented by < V-brackets >

TJ
notations <uvw> TJ TJ TJ TJ

• e.g. in a cubic system

TJ - TJ - - TJ TJ
[100] , [100] , [010] , [010] , [001] , [001] = <100>
TJ TJ TJ TJ TJ

• Family of <111> directions:

TJSame atomic arrangements
TJ along those
TJdirections TJ TJ

TJ TJ TJ TJ

33
 Linear Density
TJ TJ TJ TJ TJ
Number of atoms
Linear Density of Atoms  LD = Unit length of direction
TJ TJ TJ TJ vector TJ

[110]
TJ TJ TJ of Al in [110]
ex: linear density TJ

TJ TJ
direction
TJ TJ TJ
a = 0.405 nm
TJ TJ TJ TJ TJ

# atoms
TJ a TJ 2 TJ TJ
LD = = 3.5 nm −1

Adapted from Fig. 3.1(a),

length 2a
Callister & Rethwisch 8e.

34
 HCP Crystallographic Directions
TJ z TJ TJ
Algorithm TJ TJ

1. Vector repositioned (if necessary) to pass

TJ TJ throughTJorigin. TJ TJ
2. Read off projections in terms of unit
cell dimensions a1, a2, a3, or c
TJ a2 TJ TJ integer values TJ
3. Adjust to smallest
4. Enclose in square brackets, no commas
TJ TJ TJ TJ TJ
a3
- [uvtw] a 2
a1
TJ Adapted from Fig. 3.8(a), TJ TJ a2 TJ -a3 TJ
Callister & Rethwisch 8e. 2

ex: ½, ½, -1, 0TJ => [ 1120 ] a3

TJ TJ a1 TJ
2
dashed red lines indicate
projections onto a1 and a2 axes a1
Content in this slide will not be asked in the exam 35
 Examples of Crystallographic Directions (HCP)
TJ TJ TJ TJ TJ
z

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ
a2

TJ TJ TJ TJ TJ
-

a3
TJ TJ TJ TJ
a1

Content in this slide will not be asked in the exam

Fig. 3.8(a), Callister & Rethwisch 8e. 36
 HCP Crystallographic Directions
TJ TJ TJ TJ TJ
Hexagonal Crystals
TJ 4 parameter TJ Miller-Bravais lattice
TJ coordinates are related
TJ to TJ
the direction indices (i.e., u'v'w') as follows.
TJ TJ TJ TJ

TJ TJ 'w ' ] → [ uvtw ]

[ u 'vTJ TJ TJ

1
u= (2 u ' - v ')
TJ TJ 3 TJ TJ TJ

1
TJ TJ
v = (2 v ' - u ') TJ TJ
3
t = - (u +v )
Content in this slide will not be asked in the exam w = w'
37
 Crystallographic Planes (hkl)
TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

Adapted from Fig. 3.10,

Callister & Rethwisch 8e.
38
 Crystallographic Planes
TJ TJ TJ TJ TJ

Miller Indices: Reciprocals of the (three) axial intercepts for a

plane, cleared of TJ
TJ fractions & commonTJ multiples. All parallel
TJ TJ
planes have same Miller indices.
TJ TJ TJ TJ

TJ
Algorithm TJ TJ TJ TJ
1. Read off intercepts of plane with axes in terms of a, b, c
TJ TJ of intercepts
2. Take reciprocals TJ TJ TJ

3. Reduce to smallest integer values

TJ TJ TJ TJ
4. Enclose in parentheses, no commas i.e., (hkl)

39
 Crystallographic Planes z
TJ example
TJ a TJb c TJ TJ
1. Intercepts 1 1  c
2. Reciprocals 1/1 1/1 1/
TJ TJ TJ TJ TJ
1 1 0
3. Reduction 1 1 0 y
TJ TJ TJ
a b TJ
4. Miller Indices (110)
x
TJ TJ TJ zTJ TJ
example a b c
1. Intercepts 1/2   c
TJ TJ
2. Reciprocals 1/½ 1/ TJ
1/ TJ TJ
2 0 0
3. Reduction 2 0 0
TJ TJ TJ y TJ
4. Miller Indices (200) a b
x
40
 Crystallographic Planes
TJ TJ TJ z TJ TJ
example a b c c
TJ 1. Intercepts
TJ 1/2 1 TJ3/4 • TJ TJ
2. Reciprocals 1/½ 1/1 1/¾
•
TJ TJ 2 1 4/3 TJ
• y TJ
3. Reduction 6 3 4 a b
TJ TJ TJ TJ TJ
4. Miller Indices (634) x

TJ TJ TJ TJ TJ

TJ Family of Planes
TJ {hkl} TJ TJ

Ex: {100} = (100), (010), (001), (100), (010), (001)

41
 Crystallographic Planes (HCP)
TJ • InTJhexagonal unit cells
TJ the same ideaTJis used TJ
z

TJ TJ TJ TJ TJ
example a1 a2 a3 c
1. Intercepts 1  -1 1
TJ TJ TJ TJ
2. Reciprocals 1 1/ -1 1
1 0TJ -1 1 a2
TJ TJ TJ TJ
3. Reduction 1 0 -1 1
a3
TJ TJ TJ TJ TJ
4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.8(b),

TJ TJ TJ Callister & Rethwisch 8e. TJ

42
 Planar Density of (100) Iron
TJ TJ
Solution: At T < 912ºCTJiron has the BCC structure.
TJ TJ

2D repeat unit
TJ TJ TJ TJ TJ
(100) 4 3
a= R
3
TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ
Adapted from Fig. 3.2(c), Callister & Rethwisch 8e. Radius of iron R = 0.1241 nm
atoms
TJ
2D repeat unit 1 TJ TJ TJ
1 atoms 19 atoms
Planar Density = = 2 = 12.1 = 1.2 x 10
area a2 4 3 nm2 m2
R
2D repeat unit 3 43
 Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell
TJ TJ TJ TJ TJ
2a atoms in plane
atoms above plane
TJ TJ TJ TJ TJ
atoms below plane

TJ TJ TJ TJ
3
h= a
TJ TJ TJ TJ 2 TJ
2
 4 3  16 3 2
TJ TJ
area = 2 ah = 3TJa = 3 
2
R  = TJ R TJ
atoms  3  3
2D repeat unit 1
TJ TJ atoms =TJ 19 atomsTJ
Planar Density = = 7.0 2
0.70 x 10
area 16 3 nm m2
R2
2D repeat unit 3
44
 X-Ray Diffraction
TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

•TJDiffraction gratings TJ
must have spacing comparable
TJ to the TJ
wavelength of diffracted radiation.
• Can’t resolve spacing  
• Spacing is the distance between parallel planes of atoms. 45
 X-Rays to Determine Crystal Structure
TJ
• TJ TJ
Incoming X-rays diffract TJ
from crystal planes. TJ

TJ TJ TJ TJ TJ
reflections must
be in phase for
a detectable signal
TJ extra TJ TJ Adapted from Fig. 3.20,
TJ
 
distance
Callister & Rethwisch 8e.
travelled
TJ TJ by wave “2” TJ TJ
spacing TJ
d between
planes
TJ TJ TJ TJ TJ

Measurement of X-ray
n
TJ critical angle, TJ
c, intensity TJ d= TJ
(from 2 sin c
allows computation of
detector)
planar spacing, d.

c
46
 X-Rays to Determine Crystal Structure
TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

47
 Schematic Diagram of an X-ray Diffractometer
TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

48
 Powdered XRD
TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

49
 Problem
TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

50
 Continue…..
TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ

51
 X-Ray Diffraction Pattern
TJ TJ TJ TJ TJ
z z z
c c c
TJ TJ TJ TJ TJ
y (110) y y
a b a b a b
Intensity (relative)

TJ TJ TJ TJ
x x x (211)
TJ TJ TJ TJ TJ

TJ TJ TJ(200) TJ TJ

TJ TJ TJ TJ
Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.22, Callister 8e. 52
 SUMMARY
TJ TJ
• Atoms TJ crystalline or
may assemble into TJ TJ
amorphous structures.
TJ • Common TJ metallic crystal structures
TJ TJ
are FCC, BCC, and TJ
HCP. Coordination number and atomic packing factor
TJ are the same TJ
for both FCC and HCPTJcrystal structures. TJ

TJ
• We
TJ
can predict the density
TJ
of a material, provided
TJ
we TJ
know the atomic weight, atomic radius, and crystal
geometry (e.g., FCC, BCC, HCP).
TJ TJ TJ TJ TJ
• Crystallographic points, directions and planes are
specified in terms of indexing schemes.
TJ TJ directions and planes
Crystallographic TJ are related TJ
to atomic linear densities and planar densities.

53
 SUMMARY
TJ TJ TJ TJ TJ
• Materials can be single crystals or polycrystalline.
Material properties generally vary with single crystal
TJ TJ TJ TJ TJ
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals
TJ with randomlyTJ oriented grains. TJ TJ

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

54