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Chapter 3: The Structure of Crystalline Solids

ISSUES TO ADDRESS...
How do atoms assemble into solid structures? How does the density of a material depend on its structure? When do material properties vary with the sample (i.e., part) orientation?

Chapter 3 - 1

Energy and Packing

Non dense, ________________
Energy _______________ bond length typical neighbor bond energy r Energy typical neighbor bond length typical neighbor bond energy r

Dense, ___________________

Dense, _____________________________ to have _________ energies.

Chapter 3 - 2

Materials and Packing

Crystalline materials... atoms pack __________, 3D arrays typical of: -________ -many _________ -some _________

crystalline SiO2
Adapted from Fig. 3.23(a), Callister & Rethwisch 8e.

Noncrystalline materials... atoms have no periodic packing occurs for: - _________________ - _____________ "Amorphous" = Noncrystalline

Si

Oxygen

noncrystalline SiO2
Adapted from Fig. 3.23(b), Callister & Rethwisch 8e. Chapter 3 - 3

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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 - 4

Metallic Crystal Structures

Tend to be densely packed. Reasons for dense packing:
- Typically, only one __________is present, so all atomic ________ are the same. - Metallic bonding is not ________________. - Nearest neighbor distances tend to be small in order to __________ bond energy. - ______________ cloud shields cores from each other

Have the simplest crystal structures. We will examine three such structures...

Chapter 3 - 5

Simple Cubic Structure (SC)

Rare due to low packing density (only Po has this structure) Close-packed ___________ are cube edges.
Coordination # = ___ (# nearest neighbors)

Click once on image to start animation (Courtesy P.M. Anderson)

Chapter 3 - 6

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Atomic Packing Factor (APF)

APF = Volume of atoms in unit cell* Volume of unit cell

*assume hard spheres APF for a simple _______ structure = 0.52 atoms unit cell R=0.5a
close-packed ___________ contains 8 x 1/8 = 1 atom/unit cell
Adapted from Fig. 3.24, Callister & Rethwisch 8e.

4 3

volume atom (0.5a) 3 volume unit cell

Chapter 3 - 7

APF =

a3

Body Centered Cubic Structure (BCC)

Atoms touch each other along cube ____________.
--Note: All atoms are identical; the center atom is shaded differently only for ease of viewing.

ex: Cr, W, Fe (), Tantalum, ____________

Coordination # = 8

Click once on image to start animation (Courtesy P.M. Anderson)

Adapted from Fig. 3.2, Callister & Rethwisch 8e.

2 atoms/unit cell: 1 center + 8 _____________

Chapter 3 - 8

Atomic Packing Factor: BCC

APF for a body-centered _______ structure = 0.68
3a

a
2a
Adapted from Fig. 3.2(a), Callister & Rethwisch 8e.

Close-packed __________: length = 4R = 3 a

atoms volume 4 ( 3a/4 ) 3 2 unit cell atom 3 APF = volume a3 unit cell

Chapter 3 - 9

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Face Centered Cubic Structure (FCC)

Atoms touch each other along face ___________.
--Note: All atoms are ____________; the face-centered atoms are shaded differently only for ease of viewing.

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

Coordination # = ___

Adapted from Fig. 3.1, Callister & Rethwisch 8e. Click once on image to start animation (Courtesy P.M. Anderson)

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

Chapter 3 - 10

Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74 maximum achievable APF Close-packed directions: length = 4R = 2 a Unit cell contains: __________________ = __________________ atoms unit cell APF = 4 3 ( 2a/4 ) 3 volume atom volume unit cell
Chapter 3 - 11

2a

Adapted from Fig. 3.1(a), Callister & Rethwisch 8e.

FCC Stacking Sequence

ABCABC... __________ Sequence 2D Projection B B C A B B B A sites C C B sites B B C sites FCC _____ Cell A B C

Chapter 3 - 12

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Hexagonal Close-Packed Structure (HCP)

ABAB... Stacking Sequence 3D Projection A sites
c

2D Projection Top layer Middle layer Bottom layer __ atoms/unit cell ex: Cd, Mg, Ti, Zn
Chapter 3 - 13

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

Coordination # = ___ APF = _______ c/a = ________

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

nA VC NA

where

n = ________________________ A = atomic weight VC = ________________ = ____________ NA = Avogadros number = 6.022 x 1023 atoms/mol
Chapter 3 - 14

Theoretical Density,
Ex: Cr (BCC) A = 52.00 g/mol R = ___________ n = 2 atoms/unit cell
Adapted from Fig. 3.2(a), Callister & Rethwisch 8e.

a
52.00

a = 4R/ 3 = 0.2887 nm g mol

atoms

unit cell

theoretical = 7.18 g/cm3 actual = 7.19 g/cm3

=
volume unit cell

a3 6.022 x 1023

atoms mol
Chapter 3 - 15

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In general metals _ ceramics _ polymers 30 Why?

Metals have...
close-packing 10 (metallic bonding) often _____atomic masses

Densities of Material Classes

Metals/ Alloys
Platinum Gold, W Tantalum Silver, Mo Cu,Ni Steels Tin, Zinc Titanium Aluminum Magnesium

Graphite/ Ceramics/ Semicond

Polymers

Composites/ fibers

20

B ased on data in Table B1, Callister *GFRE, CFRE, & AFRE are Glass, Carbon, & Aramid Fiber-Reinforced Epoxy composites (values based on 60% volume fraction of aligned fibers in an epoxy matrix). Zirconia Al oxide Diamond Si nitride Glass -soda Concrete Silicon G raphite

(g/cm3 )

Ceramics have...
less _______packing often lighter elements

5 4 3 2 1

Polymers have...

PTFE Silicone PVC PET PC HDPE, PS PP, LDPE

low packing _________ (often _____________) lighter elements (C,H,O)

Glass fibers GFRE* Carbon fibers CFRE* A ramid fibers AFRE *

Composites have...
______________values

0.5 0.4 0.3

Wood Data from Table B.1, Callister & Rethwisch, 8e. Chapter 3 - 16

Crystals as Building Blocks

Some engineering applications require ________crystals:
-- diamond single crystals for abrasives
(Courtesy Martin Deakins, GE Superabrasives, Worthington, OH. Used with permission.)

-- turbine blades

Fig. 8.33(c), Callister & Rethwisch 8e. (Fig. 8.33(c) courtesy of Pratt and Whitney).

Properties of __________materials often related to crystal structure.

-- Ex: Quartz fractures more easily along some crystal planes than others.
(Courtesy P.M. Anderson)

Chapter 3 - 17

Polycrystals
Most engineering materials are ____________.

__________

1 mm Nb-Hf-W plate with an electron beam weld. Each _______ is a single crystal. If grains are _________ oriented, Grain sizes typically range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).

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

Isotropic

overall component properties are not ___________.

Chapter 3 - 18

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Single vs Polycrystals
Single Crystals
-Properties vary with direction: ____________. -Example: the __________ of elasticity (E) in BCC iron:
E (diagonal) = __________
Data from Table 3.3, Callister & Rethwisch 8e. (Source of data is R.W. Hertzberg, Deformation and Fracture Mechanics of Engineering Materials, 3rd ed., John Wiley and Sons, 1989.)

Polycrystals
-Properties may/may not vary with direction. -If grains are _________ oriented: __________.
(Epoly iron = 210 GPa)

E (edge) = 125 GPa

200 m

-If grains are _________, anisotropic.

Adapted from Fig. 4.14(b), Callister & Rethwisch 8e. (Fig. 4.14(b) is 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].)

Chapter 3 - 19

Polymorphism
Two or more distinct _______ structures for the same material (allotropy/polymorphism) iron system titanium liquid , -Ti 1538C -Fe BCC carbon 1394C __________, graphite -Fe FCC 912C BCC -Fe
Chapter 3 - 20

Crystal Systems
Unit cell: smallest __________________ which contains the complete ___________ of a crystal.
7 crystal systems 14 crystal lattices

a, b, and c are the ________ constants

Fig. 3.4, Callister & Rethwisch 8e. Chapter 3 - 21

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Point Coordinates
z c y Point ___________ for unit cell corner are 111
111

Point coordinates for ________ center are a/2, b/2, c/2

a x z

000

b 2c

b b

__________: integer multiple of lattice constants identical position in another unit cell
Chapter 3 - 22

Crystallographic Directions
z Algorithm
1. Vector ___________ (if necessary) to pass through origin. 2. Read off ____________ in terms of unit cell dimensions a, b, and c 3. Adjust to smallest ___________ values 4. Enclose in _______ brackets, no commas

y x

[uvw]

ex: ___________________________ _______________ where ___________ represents a negative index

________ of directions <uvw>

Chapter 3 - 23

Linear Density
Linear Density of Atoms LD = [110]
Number of atoms Unit length of direction vector

ex: linear _________ of Al in [110] direction a = 0.405 nm

a
Adapted from Fig. 3.1(a), Callister & Rethwisch 8e.

# atoms

LD =
length

2a

= 3.5 nm-1

Chapter 3 - 24

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HCP Crystallographic Directions

z

Algorithm
1. Vector _________ (if necessary) to pass through origin. 2. Read off projections in _________ of unit cell dimensions a1, a2, a3, or c 3. Adjust to ___________ integer values 4. Enclose in square brackets, no commas [uvtw]
a2 2

a2

a3
Adapted from Fig. 3.8(a), Callister & Rethwisch 8e.

a1

a2
-a3

ex:

____________________

a3

________ red lines indicate projections onto a1 and a2 axes

a1 2

a1
Chapter 3 - 25

HCP Crystallographic Directions

Hexagonal Crystals
4 parameter ____________ lattice coordinates are related to the direction __________ (i.e., u'v'w') as follows.
z

[ u 'v 'w ' ] [ uvtw ] u=

a2

a3 a1

1 (2 u ' - v ') 3 1 v = (2 v ' - u ') 3 t = - (u +v )

Fig. 3.8(a), Callister & Rethwisch 8e.

w = w'
Chapter 3 - 26

Crystallographic Planes

Adapted from Fig. 3.10, Callister & Rethwisch 8e. Chapter 3 - 27

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Crystallographic Planes
_____ Indices: Reciprocals of the (three) axial intercepts for a plane, cleared of _________ & common multiples. All ________ planes have same Miller indices. Algorithm
1. Read off ____________ of plane with axes in terms of a, b, c 2. Take ____________ of intercepts 3. Reduce to smallest integer values 4. Enclose in parentheses, no commas i.e., (hkl)

Chapter 3 - 28

Crystallographic Planes
z
example 1. Intercepts 2. Reciprocals 3. 4. Reduction Miller Indices a 1 1/1 1 1 _____ a 1/2 1/ 2 __ b 1/ 0 __ c 1/ 0 0 b 1 1/1 1 1 c __ ___ 0 __

c y

a x c z

example 1. Intercepts 2. Reciprocals 3. 4. Reduction Miller Indices

_____

a x

b
Chapter 3 - 29

Crystallographic Planes
z example 1. Intercepts 2. Reciprocals 3. 4. Reduction Miller Indices a 1/2 1/ 2 6 (634) b 1 1/1 1 3 c c 3/4 1/ 4/3 4 a x

Family of Planes {hkl} Ex: {100} = (100), (010), (001), (100), (010), (001)
Chapter 3 - 30

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Crystallographic Planes (HCP)

In hexagonal unit cells the same idea is used
z

example 1. Intercepts 2. Reciprocals 3. 4. Reduction

a1 1 1 1 1

a2 1/ 0 0

a3 -1 -1 -1 -1

c 1 1 1 1
a3

a2

Miller-Bravais Indices

(1011)
Adapted from Fig. 3.8(b), Callister & Rethwisch 8e.

a1

Chapter 3 - 31

Crystallographic Planes
We want to examine the ______ packing of crystallographic planes Iron foil can be used as a catalyst. The atomic packing of the exposed _________ is important.
a) Draw (100) and (111) crystallographic _____ for Fe. b) Calculate the planar ________ for each of these planes.

Chapter 3 - 32

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 and in WileyPLUS

Chapter 3 - 33

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VMSE: Metallic Crystal Structures & Crystallography Module

VMSE allows you to view crystal structures, directions, planes, etc. and manipulate them in three dimensions

Chapter 3 - 34

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
Chapter 3 - 35

VMSE: Crystallographic Planes Exercises

Additional practice on indexing crystallographic planes

Chapter 3 - 36

12

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Planar Density of (100) Iron

Solution: At T < 912C iron has the ________structure.
2D repeat unit
4 3 R 3

(100)

a=

Adapted from Fig. 3.2(c), Callister & Rethwisch 8e.

__________of iron R = 0.1241 nm

1

atoms 2D repeat unit

Planar Density =
area 2D repeat unit

a2

4 3 3

= ____

atoms atoms = ________ nm2 m2

Chapter 3 - 37

Planar Density of (111) Iron

Solution (cont): (___) plane
______ in plane/ unit surface cell

2a
nit tu

atoms in plane atoms above plane atoms _____ plane

rep

ea

2D

h=
2

3 a 2

atoms 2D repeat unit

4 3 16 3 2 area = 2 ah = 3 a 2 = 3 3 R = 3 R
atoms = = 7.0 2
R
2

Planar Density =
area 2D repeat unit

16 3 3

nm

atoms __________ m2
Chapter 3 - 38

VMSE Planar Atomic Arrangements

VMSE allows you to view planar arrangements and rotate them in 3 dimensions

BCC (110) Plane

Chapter 3 - 39

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X-Ray Diffraction

________ gratings must have spacings comparable to the wavelength of diffracted ___________. Cant resolve ____________ < Spacing is the distance between __________ planes of atoms.
Chapter 3 - 40

X-Rays to Determine Crystal Structure

Incoming X-rays _________ from crystal planes. d
et

ec

to

extra distance travelled by wave 2

t ou

go

g in

r X-

s ay

r
reflections must be in phase for a detectable signal
Adapted from Fig. 3.20, Callister & Rethwisch 8e.

________________of critical angle, c, allows computation of planar __________, d.

z c a x

X-Ray Diffraction Pattern

z c b y (110) x a b y x a c

1 g in 2 m co s in -ray X

X-ray intensity (from detector)

spacing between _________

d=

n 2 sin c

c
Chapter 3 - 41

Intensity (relative)

b
(211)

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.22, Callister 8e. Chapter 3 - 42

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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 - 43

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 - 44

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