CHAPTER 3: STRUCTURE OF CRYSTALLINE SOLIDS

Crystalline repetitive 3-D structure - all metals, many ceramics and some polymers Atomic Hard Sphere Model represent atoms as solid spheres touching each other. Lattice 3-D array of points coinciding with atom positions

METALLIC CRYSTAL STRUCTURE

Tend to be densely packed.
-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. Types: 1) FCC 2) BCC 3) HCP Focus on the unit cell: smallest repetitive entity Properties :
Coordination number number of nearest neighbor or touching atoms Atomic Packing Factor (APF) ratio of volume of atoms in unit cell to the total unit cell volume

FACE CENTERED CUBIC STRUCTURE (FCC)

Atom at each corner, and at center of each face.
--Note: All atoms are identical; the face-centered atoms are shaded differently only for ease of viewing.

ATOMIC PACKING FACTOR: FCC

APF for a body-centered cubic structure = 0.74

Coordination # = 12

Atom at each corner, and at the center of cube.

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

BODY CENTERED CUBIC STRUCTURE (BCC)

ATOMIC PACKING FACTOR: BCC

APF for a body-centered cubic structure = 0.68

Coordination # = 8

HEXAGONAL CLOSE-PACKED STRUCTURE (HCP)

ABAB... Stacking Sequence 3D Projection 2D Projection

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

A sites B sites A sites

Coordination # = 12

Top layer Middle layer Bottom layer

APF = 0.74

HCP APF
a = 2R c=2 2 a 1.633a 3

THEORETICAL DENSITY,

# atoms/unit cell

= nA VcNA Volume/unit cell

(cm3/unit cell)

Atomic weight (g/mol)

APF = 0.74

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

Example: Density Computation

Example: Compute the theoretical density of 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 = 10-7 cm) Vc = a3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10-23cm3

Characteristics of Selected Elements at 20C

Element Aluminum Argon Barium Beryllium Boron Bromine Cadmium Calcium Carbon Cesium Chlorine Chromium Cobalt Copper Flourine Gallium Germanium Gold Helium Hydrogen Symbol Al Ar Ba Be B Br Cd Ca C Cs Cl Cr Co Cu F Ga Ge Au He H

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

At. Weight (amu) 26.98 39.95 137.33 9.012 10.81 79.90 112.41 40.08 12.011 132.91 35.45 52.00 58.93 63.55 19.00 69.72 72.59 196.97 4.003 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, Callister 6e. 0.265 -----0.125 0.125 0.128 -----0.122 0.122 0.144 -----------

Polymorphism and Allotropy

Polymorphism -Having more than one crystal structure (change with T & P) -Ex. Low-Carbon Steel can exist as BCC or FCC Temperature, C

SUMMARY
Atoms may have crystalline or amorphous structures. We can predict the density of a material from the atomic weight, atomic radius, and crystal structure (e.g., FCC, BCC, HCP). Anisotropic material - properties vary with direction true for a for a single crystal orientation. Isotropic material - properties are nondirectional true for polycrystals with randomly oriented grains.

1536 1391

Liquid BCC Stable

longer heat up
FCC Stable

914
Tc 768

BCC Stable

cool down

shorter! longer! magnet falls off shorter

Allotropy -Polymorphism in elemental solid -Ex. Carbon can exist as graphite or diamond

Crystal Systems
Unit Cell: Parameters:

Crystallographic Positions (Coordinates)

- Coordinates of points expressed as fractions of unit cell dimensions

a, b, c, , ,

7 Crystal Systems: -Cubic

-Hexagonal -Tetragonal -Orthorhombic -Rhombohedral -Monoclinic -Triclini

Crystallographic Directions
-defined by line between two points Steps:
1. Translate vector to pass at origin. 2. Determine lengths of components (projections) in terms of unit cell dimensions. 3. Multiply or divide by a common factor to reduce to smallest possible integer values, uvw. 4. Direction: [uvw]

Crystallographic Planes (Miller Indices)

Steps: 1. If the plane passes through origin, translate origin. 2. Determine lengths of planar intercepts in terms of unit cell dimensions. 3. Take reciprocals of the numbers in Step 2. 4. Multiply or divide by a common factor to reduce to integers: hkl 5. Enclose: (hkl) Example:

Family of Directions nonparallel directions which are equivalent (same atom spacing). Ex. Cubic: <100> family [100], [010], [001] Tetragonal <100> - [100], [010]

Planes for Hexagonal Crystals Four axes: 1 , 2 , 3 , z

Example:

Linear Density fraction of the length of the line intersected by atoms. Planar Density - Fraction of the area occupied by atoms (count atoms only if plane intersect its center.
Example: For simple cubic crystal, find: 1. Linear density for [111] direction, 2. Planar density for (100) plane.

X-RAYS TO CONFIRM CRYSTAL STRUCTURE

Incoming X-rays diffract from crystal planes.
de

te

extra distance travelled by wave 2

t ou

in go

ys ra X-

ct or

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

1 g in 2 m co ys in - r a 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