Chapter 3 The Structure of Crystalline Solids

EGN 3365 Materials I

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Objectives of Chapter 3

Learn classification of materials based on atomic/ionic arrangements Describe the arrangements in crystalline solids based on lattice, basis, and crystal structure

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Issues to Address

How do atoms assemble into solid structures? How do the structures of metals differ from those of other materials? How does the density of a material depend on its structure?

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Types of Solids

Crystalline Material:

Atoms self-organize in a periodic array Single Crystal: Atoms are in a repeating or periodic array over the entire extent of the material Polycrystalline Material: Comprised of many small crystals or grains Lacks atomic arrangement

Amorphous Material:

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Materials and Packing

Figure: Levels of atomic arrangements in materials: (a) NO ORDER - Inert monoatomic gases have no regular ordering of atoms: (b,c) SHORT RANGE ORDER (SRO) - Some materials, including water vapor, nitrogen gas, amorphous silicon and silicate glass have short-range order. (d) LONG-RANGE ORDER (LRO) - Metals, alloys, many ceramics and some polymers have regular ordering of atoms/ions that extends through the material.

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Single Crystals vs. Polycrystalline Materials

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Classification of Materials Based on Structure

Figure 3.4 (a) Photograph of a silicon single crystal. (b) Micrograph of a polycrystalline stainless steel showing grains and grain boundaries (Courtesy Dr. M. Hua, Dr. I. Garcia, and Dr. A.J. Deardo.)

Classification of Materials Based on Structure

Figure: Liquid crystal display. These materials are amorphous in one state and undergo localized crystallization in response to an external electric field and are widely used in liquid crystal displays. (Courtesy of Nick Koudis/PhotoDisc/Getty Images.)

Materials and Packing Summary

(c) 2003 Brooks/Cole Publishing / Thomson Learning

Crystal Structure

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Lattice Collection of points that divide space into smaller equally sized segments Basis Group of atoms associated with a lattice point Unit cell Subdivision of the lattice that still retains the overall characteristics of the entire lattice Atomic radius Apparent radius of an atom Typically calculated from the dimensions of the unit cell, using closepacked directions (depends upon coordination number for metals, each atom has the same number of nearest-neighbor or touching atoms) Packing factor The fraction of space in a unit cell occupied by atoms.
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Definitions

Unit Cell

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The fourteen types of lattices grouped in seven crystal systems.

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Metallic Crystal Structures

Metals are usually (poly)crystalline; although formation of amorphous metals is possible by rapid cooling As we learned in Chapter 2, the atomic bonding in metals is non-directional no restriction on numbers or positions of nearest-neighbor atoms large number of nearest neighbors and dense atomic packing Atomic (hard sphere) radius, R, defined by ion core radius typically 0.1 - 0.2 nm The most common types of unit cells are the faced-centered cubic (FCC), the body-centered cubic (BCC) and the hexagonal close-packed (HCP).
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Simple Cubic Cell (SCC)

Rare due to poor packing (only Po has this structure) Close-packed directions are cube edges.
Coordination # = 6 (# nearest neighbors)

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(Courtesy P.M. Anderson)

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Atomic Packing Factor (APF)

Volume of atoms in unit cell* APF = Volume of unit cell *assume hard spheres APF for a simple cubic structure = 0.52 atoms unit cell R=0.5a
close-packed directions contains 8 x 1/8 = 1 atom/unit cell
Adapted from Fig. 3.23, Callister 7e.

APF =

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

Body Centered Cubic Cell (BCC)

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

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

Coordination # = 8

(Courtesy P.M. Anderson)

2 atoms/unit cell: 1 center + 8 corners x 1/8

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Atomic Packing Factor: BCC

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

a
2a

Adapted from Fig. 3.2(a), Callister 7e.

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

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

Face Centered Cubic Cell (FCC)

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

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

Coordination # = 12

Adapted from Fig. 3.1, Callister 7e. (Courtesy P.M. Anderson)

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

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Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74 maximum achievable APF Close-packed directions: length = 4R = 2 a 2a Unit cell contains: 6 x 1/2 + 8 x 1/8 = 4 atoms/unit cell atoms volume 4 ( 2a/4) 3 4 unit cell atom 3 APF = volume a3 unit cell

a
Adapted from Fig. 3.1(a), Callister 7e.

Determining the Relationship between Atomic Radius and Lattice Parameters

Determine the relationship between the atomic radius and the lattice parameter in SC, BCC, and FCC structures when one atom is located at each lattice point.

(c) 2003 Brooks/Cole Publishing / Thomson Learning

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We find that atoms touch along the edge of the cube in SC structures.

a0

= 2r

In BCC structures, atoms touch along the body diagonal. There are two atomic radii from the center atom and one atomic radius from each of the corner atoms on the body diagonal, so

a0

4r = 3

In FCC structures, atoms touch along the face diagonal of the cube. There are four atomic radii along this lengthtwo radii from the facecentered atom and one radius from each corner, so:

a0
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4r = 2

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FCC Stacking Sequence

ABCABC... Stacking Sequence 2D Projection B B C A B B B A sites C C B sites B B C sites A B C

FCC Unit Cell

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Theoretical Density

Example: Copper
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)

Result: theoretical Cu = 8.89 g/cm 3 Compare to actual: Cu = 8.94 g/cm 3

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Theoretical Density,

Ex: Cr (BCC) A = 52.00 g/mol R = 0.125 nm n=2

R
atoms unit cell

a
2 52.00

a = 4R/ 3 = 0.2887 nm g mol

=
volume unit cell

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

a3 6.023 x 1023

atoms mol

Determining the Density of BCC Iron

Determine the density of BCC iron, which has a lattice parameter of 0.2866 nm. SOLUTION Atoms/cell = 2, a0 = 0.2866 nm = 2.866 10-8 cm Atomic mass = 55.847 g/mol Volume of unit cell = cm3/cell = (2.866 10-8 cm)3 = 23.54 10-24 a0
3

Avogadros number NA = 6.02 1023 atoms/mol

(number of atoms/cell)(atomic mass of iron) Density = (volume of unit cell)(Avogadro' s number) (2)(55.847) 3 = 7 . 882 g / cm = (23.54 10 24 )(6.02 10 23 )
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Densities of Material Classes

metals ceramics polymers Why?
Metals have...
close-packing (metallic bonding) large atomic mass

Ceramics have...
less dense packing (covalent bonding) often lighter elements

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

Composites have...
intermediate values
-36Data from Table B1, Callister 6e.

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