Crystal Structures

Chapter 3

Atomic Arrangements
In gases there is no order
In liquids there is short range order In solids there is long range range The order is determined by the type of atomic

bonds

Lattices
A grid like pattern
Composed of unit cells Unit cells are stacked together endlessly to form

the lattice (with no empty spaces between cells)

Scanning Tunneling Microscope Image of Iron in the (110) plane

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Unit Cells
There are seven basic shapes of the unit cells
Defined by lattice parameters

The edge lengths Angles

14 Bravais lattices

Cubic Unit Cells

Simplest to understand
Simple (SC)

One atom per unit cell

Body Centered (BCC)

Two atoms per unit cell

Face Centered (FCC)

4 atoms per unit cell

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Simple Cubic
r r

ao

ao = 2r

Face Centered Cubic (FCC)

a0 a0

2a 0 4r
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Body Centered Cubic (BCC)

2a 0
3a 0
a0

3a 0 4r
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Coordination Number
The number of touching neighbors
SC is 6 BCC is 8 FCC is 12

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Density
r

m/V m = #atoms * Atomic Weight Avogadros number V = edge length ^3

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Packing Factor
The fraction of the cell that is filled up with atom

(The rest is empty) Packing Factor = Atom volume Cell volume

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Hexagonal Packing
Hexagonal close packing (ababab)
Hexagonal cubic packing (abcabc) Hexagonal cubic packing is the same as FCC!

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Typical Arrangements

Metals
BCC FCC HCP

Ceramics
Simple Cubic FCC HCP

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Allotropic Transformations
Many materials have more than one crystal structure Ex. Carbon

Graphite Diamond Buckyball

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Allotropic Transformation
Iron

- ferrite) FCC at moderate temperatures (austenite) BCC at low temperatures (a - ferrite) Change in specific volume
BCC at high temperatures (d

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Specific Volume
May be familiar with this term from Thermo
Inverse of density v=1/r m3/kg Its the amount of volume a unit mass uses

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Coordinate Systems
For cubic cells a rectangular coordinate system

makes sense. For non cubic systems it makes more sense for the coordinates to be parallel to the edges of the unit cell. It also makes sense to use the edge length (lattice parameter) as the distance measurement.
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Coordinates
Z

1,1,1

Y
X

0,0,0

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Directions
Z [0 1 0] [1 0 1]

Y
X
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Miller Indices
Take the coordinates of the head and subtract the coordinates of the tail Clear fractions by multiplying through by an integer Or reduce by dividing through by an integer Signify a negative value by drawing a line above the value Ex. [ 1 0 0 ] Direction, not a line segment

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Negatives
Because we are determining a direction, the

negative of the vector is not the same as the positive they are two different directions!!

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Note
All the edges have a similar Miller index

<1 0 0>
All the face diagonals have a similar Miller index

<1 1 0>
All the body diagonals have a similar Miller index

<1 1 1> < > indicate a family of directions, called directions of a form
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Linear Properties
Linear Density

# of atoms/unit length
Repeat Distance

Distance between the center of adjacent atoms Inverse of Linear Density

Linear Packing Fraction

Linear Distance covered by atoms distance between the atoms

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Planes
Planar Miller indices can also be used to describe a plane. Find the places where the plane crosses each axis (If necessary move the coordinate system so the plane does not go through the origin. Invert Clear fractions Express with ( )

Ex (1 1 1)
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For example..
Z ( 1 1 1)

Y
X
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Planes of a form
All faces of the cell are of the form

{100}
All perpendicular diagonal planes are of the form

{110}
All body diagonal planes are of the form

{1 1 1}

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Negatives
Although vectors with opposite signs are

different directions, planes with opposite signs are the same!!

Z
Z

Y X X

Y
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Interstitial Sites
There are always holes in a crystal matrix
Size of the holes depends on how the atoms are

ordered
Tetrahedral 4 atoms surround the hole Octahedral 6 atoms surround the hole (Why the name?) Cubic 8 atoms surround the hole
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Simple Cubic
Cubic holes

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Face Centered Cubic

Both tetrahedral and octahedral holes
Small atoms can fit in the tetrahedral holes,

whereas bigger atoms can fit in the octahedral holes

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Body Centered Cubic

Also both tetrahedral and octahedral holes
The holes in the BCC crystal are not symmetrical (Prove it to yourself)

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Why do we care about the holes in crystal lattices?

Alloying elements and impurities can fit in the

holes

C fits into the holes in the Fe lattice Most metals are permeable to hydrogen and helium
Ceramic Crystals are made with one ion forming

the lattice, and the other ion in the holes The ions need to fit snugly, so they squeeze into holes that are not quite big enough
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Radius Ratio
Coordination # Name 12 FCC or HCP
8 Cubic

Smallest r/R
1.00 (substitution) 0.732 1.00

6 Octahedral
4 Tetrahedral

0.414 0.732
0.225 0.414
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Ionic Crystals
Sodium Chloride Structure
FCC 1:1 ratio of cation to anion What is the radius ratio of Na+ to Cl- ?

Find the ionic radii on the periodic table r/R = 0.54

Need an octahedral hole!!
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Sodium Chloride
Is there any macroscopic evidence that salt

forms a cubic crystal? Use a magnifying glass and check it out yourself

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Ionic Crystals
Cesium Chloride Structure
Simple Cubic 1:1 ratio of the cation to anion Why isnt it the same as NaCl? What is the ionic radius ratio?

r/R = 0.92
Need a cubic hole
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More Ionic Crystals

Flourite CaF2
FCC r/R = 0.74 Requires a cubic hole But There is

only one Ca++ for every 2 F So Only half the cells have Ca in the middle
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Flourite
Can be thought of as FCC with Ca++ defining the lattice and F- in the tetrahedral holes. This approach offers the advantage that all of the unit cells are the same.

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Ionic Crystals
Zinc Blende ZnS
r/R = 0.4 Requires a tetrahedral hole Only half of the tetrahedral holes are filled

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Other Ionic and Covalent Crystals

Diamond is covalently bonded C

FCC An additional C in half of the tetrahedral sites Similar to ZnS and SiO2 Check out the model in the room

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Other models
CaCO3 (marble or limestone)
CO2

Quartz

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The fourteen types of Bravais lattices grouped in seven crystal systems.

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Characteristics of crystal system

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Definition of the lattice parameters and their use in cubic, orthorhombic, and hexagonal crystal systems

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Illustration of coordinations in (a) SC and (b) BCC unit cells

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The hexagonal close-packed (HCP) structure (left) and its unit cell
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Crystal Structure Characteristics

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