COMPLEX CRYSTAL STRUCTURES

We will develop approaches to visualize, rationalize and understand more complex crystal structures

Outline:

Naming crystal structures

The Eutactic Framework

Aspects of Close-packing ( FCC, HCP, BCC )

Simple stacking in FCC and HCP

Interstitial sites in close-packed structures

Examples of complex crystals in the eutectic framework

Other ways to consider crystals:

Polyhedral complexes

Stacking of more complex objects

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Naming crystal structures:

1. Archetype

2. Strukturbericht

A: elements (A1 = , A2 = , A3 = , A4 = …. A15)

B: 1:1 alloys/compounds (B1 = NaCl, B2 = CsCl, B3 = zinc blende, B4 = wurtzite …)

C: 2:1 alloys/compounds

D: other stoichiometry (D0n, D1n,…D10n)

E: ternaries

L: ordered alloys (there are 6, incl. L10, L12)

There is a list in your text, pg. 144

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Eutactic Framework Approach: a way to “make” more complex crystals

Start with FCC, HCP or BCC “framework”:

1. substitute atoms is a specific ordered arrangement ON the framework

(“superlattice” sites)

and/or:

2. populate the interstitial sites in specific ways, to varying degrees

Notes:

Framework atoms need no longer touch one another

Frameworks may distort away from the ideal shape (e.g., cubic)

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Close-Packed Structures are Special

Hexagonal Close-Packed (HCP) Face-Centered Cubic (FCC) Body-Centered Cubic (BCC)

P63mmc Fm3m Im3m

2 atoms per primitive UC: 4 atoms per conv. UC: 2 atoms per conv. UC:
0,0,0 0,0,0 0,0,0
1/3, 2/3, 1/2 1/2, 1/2, 0… 1/2, 1/2, 1/2

APF = 0.74 APF = 0.74 APF = 0.68

CN = 12 CN = 12 CN = 8

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Crystals via Stacking of Close-Packed
Layers of Spheres

A A
C C
B B B
A A A
C C C
B B
A A

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Crystals via Stacking of Close-Packed
Layers of Spheres

A A
C C
B B B
A A A
C C C
B B
A A

6
Crystals via Stacking of Close-Packed
Layers of Spheres

A A
C C
B B B
A A A
C C C
B B
A A

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Crystals via Stacking of Close-Packed
Layers of Spheres

A A
C C
B B B
A A A
C C C
B B
A A

8
Crystals via Stacking of Close-Packed
Layers of Spheres

A A
C C
B B B
A A A
C C C
B B
A A

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Crystals via Stacking of Close-Packed
Layers of Spheres

Stacking close-packed planes A-B-C leads to FCC!

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Crystals via Stacking of Close-Packed
Layers of Spheres

A A
C C
B B B
A A A
C C C
B B
A A

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Crystals via Stacking of Close-Packed
Layers of Spheres

A A
C C
B B B
A A A
C C C
B B
A A

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Crystals via Stacking of Close-Packed
Layers of Spheres

A A
C
B B
A A A
C C
B
A A

Stacking close-packed planes

A-B-A-B leads to HCP 13
Interstitial Sites in Crystals

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Interstitial sites in an FCC crystal

How many tetrahedral interstitial sites per unit cell?

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Interstitial sites in an FCC crystal

How many octahedral sites per unit cell?

What is the radius of the octahedral site in a hard sphere model?

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Interstitial sites in Cubic I lattice (BCC crystal)

Distorted octahedral interstitial site

What is the minimum radius of the interstitial site in a hard sphere model?

How many of these sites per unit cell? 17

 Diamond Cubic and Zinc Blende (archetypes) are simple examples where
interstitial sites are populated in regular fashion to create a new crystal structure.

Diamond Cubic: FCC with 2-atom basis: 0,0,0 and 1/4, 1/4, 1/4

Eutactic Description:
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Does BCC have a tetrahedral interstitial site?

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Does BCC have a tetrahedral interstitial site?

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 What kind of interstitials
are in HCP?

Recall that FCC has O and T interstitials…

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 What kind of interstitial
sites in HCP?

A A
C C
B B B
A A A
C C C
B B
A A A

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 What kind of interstitial
sites in HCP?

A A
C C
B B B
A A A
C C C
B B
A A A

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 What kind of interstitial
sites in HCP?

A A
C C
B B B
A A A
C C C
B B
A A A

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 What kind of interstitial
sites in HCP?
what kind of site is this?

B
A A A
C
B B
A A A

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 What kind of interstitial
sites in HCP?
what kind of site is this?

B
A A A
C
B B
A A A

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Eutactic Framework Approach: a way to “make” more complex crystals

Start with FCC, HCP or BCC “framework”:

1. substitute atoms is a specific ordered arrangement ON the framework

(“superlattice” sites)

and/or:

2. populate the interstitial sites in specific ways, to varying degrees

Notes:

Framework atoms need no longer touch one another

Frameworks may distort away from the ideal shape (e.g., cubic)

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L10 (“CuAu”):

1. How do we describe this in the eutactic approach?

2. What is the crystal system of L10? How are atom positions specified?
3. Will properties be similar just below vs. just above the order-disorder
T?
4. How is an ordered structure different from a compound? 28
The Ti - Al system:
D022
A2
L10

A3
D019
A1

Based on the phase diagram, what eutactic structure might you predict
for D019?

See Rohrer, pg. 155, for the crystal plan — convince yourself that this is
a substituted HCP (no interstitials).
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