CHAPTER 3: CRYSTAL STRUCTURES & PROPERTIES

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

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Crystal Structure
Motivation: Many of the properties of materials (especially mechanical) are determined by the arrangement of the atoms. This arrangement is called the materials crystal structure. An important distinction Atomic structure relates to the number of protons and neutrons in the nucleus of an atom, as well as the number and probability distributions of the electrons. Crystal structure pertains to the arrangement of atoms in the crystalline solid material.

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 Atoms can be arranged either in a regular, periodic array (i.e., long-range order) or completely disordered (amorphous). We need a way to specify crystallographic directions and planes. c
To illustrate the concept of crystal structure and lattice systems, we first identify a coordinate system (x, y, z):
a

z x y b

We cant specify directions or planes without knowing what the reference system is.
MECH 221 PM Wood-Adams Fall 2008

What is the Unit Cell?

The unit cell is the smallest group of atoms

which can generate the entire crystal by translation.

Definition: the length of each unit cell axis is called a lattice parameter. In cubic systems, all three orthogonal lattice parameters are equal Lattice parameters are typically on the order of a few Angstroms (or a few tenths of a nanometer)
MECH 221 PM Wood-Adams Fall 2008

ENERGY AND PACKING

Non dense, random packing
Energy typical neighbor bond length typical neighbor bond energy r

Dense, regular packing

Energy typical neighbor bond length

typical neighbor bond energy

Dense, regular-packed structures tend to have lower energy.

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MATERIALS AND PACKING

Crystalline materials... atoms pack in periodic, 3D arrays typical of: -metals -many ceramics -some polymers

crystalline SiO2
Adapted from Fig. 3.18(a),

Callister 6e.

Noncrystalline materials... atoms have no periodic packing occurs for: -complex structures -rapid cooling "Amorphous" = Noncrystalline
MECH 221 PM Wood-Adams

Si

Oxygen

noncrystalline SiO2
Adapted from Fig. 3.18(b),

Callister 6e.

Fall 2008

METALLIC CRYSTALS
tend to be densely packed. have several 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. have the simplest crystal structures. We will look at three such structures...
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SIMPLE CUBIC STRUCTURE (SC)

Rare due to poor packing (only Po has this structure) Close-packed directions are cube edges.

In terms of the hard sphere model we say the atoms are touching in the close-packed directions!

Coordination # = 6 (# nearest neighbors)

(Courtesy P.M. Anderson)

MECH 221

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ATOMIC PACKING FACTOR

APF = Volume of atoms in unit cell* Volume of unit cell *assume hard spheres

APF for a simple cubic structure = 0.52

a R=0.5a
close-packed directions contains 8 x 1/8 = 1 atom/unit cell
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atoms unit cell APF =

volume atom 4 (0.5a)3 1 3 a3 volume unit cell

6

Adapted from Fig. 3.19, Callister 6e.

PM Wood-Adams

Fall 2008

BODY CENTERED CUBIC STRUCTURE (BCC)

Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded differently only for ease of viewing.

Coordination # = 8

Adapted from Fig. 3.2,

Callister 6e.

(Courtesy P.M. Anderson)

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ATOMIC PACKING FACTOR: BCC

APF for a body-centered cubic structure = 0.68

Close-packed directions: length = 4R = 3a Unit cell contains: 1 + 8 x 1/8 = 2 atoms/unit cell

a

R
Adapted from Fig. 3.2,

Callister 6e.

atoms volume 4 3 ( 3a/4) 2 unit cell atom 3 APF = volume 3 a unit cell
PM Wood-Adams Fall 2008

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FACE CENTERED CUBIC STRUCTURE (FCC)

Close packed directions are face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded differently only for ease of viewing.

Coordination # = 12

Adapted from Fig. 3.1(a),

Callister 6e.

(Courtesy P.M. Anderson)

MECH 221

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ATOMIC PACKING FACTOR: FCC

APF for a body-centered cubic structure = 0.74

Adapted from Fig. 3.1(a),

Callister 6e.

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FCC STACKING SEQUENCE

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

A B C

close-packed plane of atoms

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HEXAGONAL CLOSE-PACKED STRUCTURE (HCP)

ABAB... Stacking Sequence 3D Projection
A sites B sites A sites
Adapted from Fig. 3.3,

2D Projection

Top layer Middle layer Bottom layer

Callister 6e.

Coordination # = 12 APF = 0.74

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THEORETICAL DENSITY,
# atoms/unit cell

= nA VcNA Volume/unit cell

(cm3/unit cell)

Atomic weight (g/mol)

Avogadro's number (6.023 x 10 23 atoms/mol)

Example: Copper

Data from Table inside front cover of Callister (see next slide): crystal structure = FCC: 4 atoms/unit cell atomic weight = 63.55 g/mol (1 amu = 1 g/mol) atomic radius R = 0.128 nm (1 nm = 10-7cm) Vc = a3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10-23cm3

Result: theoretical Cu = 8.89 g/cm3 Compare to actual: Cu = 8.94 g/cm3

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Characteristics of Selected Elements at 20C

At. Weight Symbol (amu) Element Aluminum Al 26.98 Ar Argon 39.95 Ba Barium 137.33 Be Beryllium 9.012 B Boron 10.81 Br Bromine 79.90 Cd Cadmium 112.41 Ca Calcium 40.08 C Carbon 12.011 Cs Cesium 132.91 Cl Chlorine 35.45 Chromium Cr 52.00 Co Cobalt 58.93 Cu Copper 63.55 F Flourine 19.00 Ga Gallium 69.72 Germanium Ge 72.59 Au Gold 196.97 He Helium 4.003 H Hydrogen 1.008 Density (g/cm3) 2.71 -----3.5 1.85 2.34 -----8.65 1.55 2.25 1.87 -----7.19 8.9 8.94 -----5.90 5.32 19.32 ----------Crystal Structure FCC -----BCC HCP Rhomb -----HCP FCC Hex BCC -----BCC HCP FCC -----Ortho. Dia. cubic FCC ----------Atomic radius (nm) 0.143 -----0.217 0.114 Adapted from -----Table, "Charac-----teristics of 0.149 Selected Elements", 0.197 inside front 0.071 cover, 0.265 Callister 6e. -----0.125 0.125 0.128 -----0.122 0.122 0.144 ----------15

Polymorphism and allotropy

Carbon is a good example of allotropy, it has 3 crystal structures with very different properties.

From Principles of Electronic Materials and Devices 2nd Ed., S.O. Kasap, McGraw-Hill

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DENSITIES OF MATERIAL CLASSES

metals > ceramics >polymers
Why?
Metals have...
close-packing (metallic bonding) large atomic mass
30 20
Platinum Gold, W Tantalum Silver, Mo Cu,Ni Steels Tin, Zinc Titanium Aluminum Magnesium

Metals/ Alloys

Graphite/ Ceramics/ Polymers Semicond

Composites/ fibers

10

Based 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 Graphite

Ceramics have...

(g/cm3)

less dense packing (covalent bonding) often lighter elements

5 4 3 2 1

Glass fibers PTFE Silicone PVC PET PC HDPE, PS PP, LDPE GFRE* Carbon fibers CFRE* Aramid fibers AFRE*

Polymers have...

poor packing (often amorphous) lighter elements (C,H,O)

Composites have...
intermediate values
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0.5 0.4 0.3

Wood

Data from Table B1, Callister 6e.

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 Some engineering applications require single crystals:

--diamond single crystals for abrasives --turbine blades
Fig. 8.30(c), Callister 6e. (Fig. 8.30(c) courtesy of Pratt and Whitney). (Courtesy Martin Deakins, GE Superabrasives, Worthington, OH. Used with permission.)

CRYSTALS AS BUILDING BLOCKS

Crystal properties reveal features of atomic structure.

--Ex: Certain crystal planes in quartz fracture more easily than others.
(Courtesy P.M. Anderson)

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Single crystals of fluorite

Fluorite is a ceramic with a unit cell made up of 8 cubes

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 Most engineering materials are polycrystals.

POLYCRYSTALS

1 mm

Adapted from Fig. K, color inset pages of Callister 6e. (Fig. K is courtesy of Paul E. Danielson, Teledyne Wah Chang Albany)

Nb-Hf-W plate with an electron beam weld. Each "grain" is a single crystal. If crystals are randomly oriented,
overall component properties are not directional.

Crystal sizes typ. range from 1 nm to 2 cm

(i.e., from a few to millions of atomic layers).
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Solidification of a polycrystalline material

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Fall 2008

SINGLE VS POLYCRYSTALS
Single Crystals
-Properties vary with direction: anisotropic. -Example: the modulus of elasticity (E) in BCC iron:
E (diagonal) = 273 GPa
Data from Table 3.3, Callister 6e. (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 randomly oriented: isotropic.
(Epoly iron = 210 GPa)

E (edge) = 125 GPa

200 m

-If grains are textured, anisotropic.

MECH 221 PM Wood-Adams

Adapted from Fig. 4.12(b), Callister 6e. (Fig. 4.12(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].)

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X-RAYS TO CONFIRM CRYSTAL STRUCTURE

Incoming X-rays diffract from crystal planes.
de te ct or s y ra

extra distance travelled by wave 2

Measurement of:
Critical angles, c, for X-rays provide atomic spacing, d.

Read more about this subject in the text book. Learn how to use Braggs Law.
MECH 221 PM Wood-Adams

1 g in 2 m c o ys in ra X-

ut o

g in go

X-

reflections must be in phase to detect signal

Adapted from Fig. 3.2W, Callister 6e.

spacing d between planes

x-ray intensity (from detector)

d=n/2sinc

c
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SCANNING TUNNELING MICROSCOPY

Atoms can be arranged and imaged!
Photos produced from the work of C.P. Lutz, Zeppenfeld, and D.M. Eigler. Reprinted with permission from International Business Machines Corporation, copyright 1995.

Carbon monoxide molecules arranged on a platinum (111) surface.

Iron atoms arranged on a copper (111) surface. These Kanji characters represent the word atom.
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MECH 221

DEMO: HEATING AND COOLING OF AN IRON WIRE

Demonstrates "polymorphism"
Temperature, C 1536 1391
longer heat up
FCC Stable Liquid BCC Stable

The same atoms can have more than one crystal structure.

914
Tc 768

BCC Stable

cool down

shorter! longer! magnet falls off shorter

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SUMMARY
Atoms may assemble into crystalline or amorphous 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). Material properties generally vary with single crystal orientation (i.e., they are anisotropic), but properties are generally non-directional (i.e., they are isotropic) in polycrystals with randomly oriented grains.
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