Structure of Solids

Dr. K. Jayanarayanan
POLYCRYSTALLINE MATERIALS
• “Nuclei” form during solidification, each of which grows into crystals
 SOME DEFINITIONS …
• Lattice: 3D array of regularly
spaced points
• Crystalline material: atoms
situated in a repeating 3D
periodic array over large atomic
distances
• Amorphous material: material
with no such order
• Hard sphere representation:
atoms denoted by hard, touching
spheres
• Reduced sphere representation
• Unit cell: basic building block unit
(such as a flooring tile) that
repeats in space to create the
crystal structure; it is usually a
parallelepiped or prizm
CRYSTAL SYSTEMS
 METALLIC CRYSTALS
• tend to be densely packed.
• have several reasons for dense packing:
-Typically, made of heavy element.
-Metallic bonding is not directional; i.e., no
restrictions as to the number and position of
nearest-neighbor atoms
-Nearest neighbor distances tend to be small in
order to lower bond energy.

• have the simplest crystal structures.

We will look at four such structures...
SIMPLE CUBIC STRUCTURE (SC)
• Cubic unit cell is 3D repeat unit
• Rare (only Po has this structure)
• Close-packed directions (directions along which atoms touch each other)
are cube edges.
• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

 ATOMIC PACKING FACTOR
• Fill a box with hard spheres
– Packing factor = total volume of spheres in
box / volume of box
– Question: what is the maximum packing factor
you can expect?
• In crystalline materials:
– Atomic packing factor = total volume of atoms
in unit cell / volume of unit cell
– (as unit cell repeats in space)
 ATOMIC PACKING FACTOR
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres

a volume
atoms atom
R=0.5a unit cell 4
1 (0.5a) 3
3
close-packed directions
APF =
contains 8 x 1/8 = a3 volume
1 atom/unit cell unit cell
Adapted from Fig. 3.19,
Callister 6e.

Lattice constant
• APF for a simple cubic structure = 0.52
 BODY CENTERED CUBIC
STRUCTURE (BCC)
• Coordination # = 8

Adapted from Fig. 3.2,

(Courtesy P.M. Anderson) Callister 6e.

• Close packed directions are cube diagonals.

--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.
ATOMIC PACKING FACTOR: BCC
Close-packed directions:
length = 4R
= 3a
Unit cell c ontains:
1 + 8 x 1/8
= 2 atoms/unit cell
R
Adapted from a
Fig. 3.2,
Callister 6e. atoms volume
4
unit cell 2 ( 3a/4 ) 3
3 atom
APF =
volume
a3
unit cell
• APF for a body-centered cubic structure = 3/8 = 0.68
 FACE CENTERED CUBIC
STRUCTURE (FCC)
• Coordination # = 12

Adapted from Fig. 3.1(a),

(Courtesy P.M. Anderson) Callister 6e.

• Close packed directions are face diagonals.

--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
ATOMIC PACKING FACTOR: FCC
Close-packed directions:
length = 4R
= 2a
Unit cell c ontains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 6e. atoms volume
4
unit cell 4 ( 2a/4 ) 3
3 atom
APF =
volume
a3
unit cell
• APF for a body-centered cubic structure = /(32) = 0.74
(best possible packing of identical spheres)
 HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

B sites Middle layer

A sites Bottom layer

Adapted from Fig. 3.3,
Callister 6e.

• Coordination # = 12
• APF = 0.74, for ideal c/a ratio of 1.633
 COMPARISON OF CRYSTAL
STRUCTURES

Crystal structure coordination # packing factor close packed

directions

• Simple Cubic (SC) 6 0.52 cube edges

• Body Centered Cubic (BCC) 8 0.68 body diagonal

• Face Centered Cubic (FCC) 12 0.74 face diagonal

• Hexagonal Close Pack (HCP) 12 0.74 hexagonal side

 THEORETICAL DENSITY, 
Density = mass/volume

mass = number of atoms per unit cell * mass of each atom

mass of each atom = atomic weight/avogadro’s number

# atoms/unit cell Atomic weight (g/mol)

 nA
Volume/unit cell Vc N A Avogadro's number
(cm 3 /unit cell) (6.023 x 10 23 atoms/mol)
Characteristics of Selected Elements at 20C
At. Weight Density Crystal Atomic radius
Element Symbol (amu) (g/cm 3 ) Structure (nm)
Aluminum Al 26.98 2.71 FCC 0.143
Argon Ar 39.95 ------ ------ ------
Barium Ba 137.33 3.5 BCC 0.217
Beryllium Be 9.012 1.85 HCP 0.114
Boron B 10.81 2.34 Rhomb ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ ------ teristics of
Cadmium Cd 112.41 8.65 HCP 0.149 Selected
Elements",
Calcium Ca 40.08 1.55 FCC 0.197 inside front
Carbon C 12.011 2.25 Hex 0.071 cover,
Cesium Cs 132.91 1.87 BCC 0.265 Callister 6e.
Chlorine Cl 35.45 ------ ------ ------
Chromium Cr 52.00 7.19 BCC 0.125
Cobalt Co 58.93 8.9 HCP 0.125
Copper Cu 63.55 8.94 FCC 0.128
Flourine F 19.00 ------ ------ ------
Gallium Ga 69.72 5.90 Ortho. 0.122
Germanium Ge 72.59 5.32 Dia. cubic 0.122
Gold Au 196.97 19.32 FCC 0.144
Helium He 4.003 ------ ------ ------
Hydrogen H 1.008 ------ ------ ------
 THEORETICAL DENSITY, 
# atoms/unit cell Atomic weight (g/mol)

 nA
Volume/unit cell Vc N A Avogadro's number
(cm 3 /unit cell) (6.023 x 10 23 atoms/mol)

Example: Copper
Data from Table inside front cover of Callister (see previous 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 = a 3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10 -23 cm 3
Result: theoretical Cu = 8.89 g/cm 3
Compare to actual: Cu = 8.94 g/cm 3
 CRYSTAL SYSTEMS

• Based on shape of unit cell ignoring actual atomic

locations
• Unit cell = 3-dimensional unit that repeats in space
• Unit cell geometry completely specified by a, b, c &
lattice parameters or lattice constants)
• Seven possible combinations of a, b, c & , resulting
in seven crystal systems
 CRYSTAL STRUCTURES
• Plenty of crystal structures available at:
http://cst-www.nrl.navy.mil/lattice/

• Polymorphism
– Same compound occurring in more than one crystal
structure

• Allotropy
– Polymorphism in elemental solids (e.g., carbon)
 CRYSTALLOGRAPHIC POINTS,
DIRECTIONS & PLANES
• In crystalline materials, often necessary to specify points,
directions and planes within unit cell and in crystal lattice
• Three numbers (or indices) used to designate points,
directions (lines) or planes, based on basic geometric
notions
• The three indices are determined by placing the origin at
one of the corners of the unit cell, and the coordinate
axes along the unit cell edges
 POINT COORDINATES
• Any point within a unit cell specified as fractional
multiples of the unit cell edge lengths
• Position P specified as q r s; convention:
coordinates not separated by commas or
punctuation marks
EXAMPLE: POINT COORDINATES
• Locate the point (1/4 1 ½)

• Specify point coordinates for all atom

positions for a BCC unit cell
– Answer: 0 0 0, 1 0 0, 1 1 0, 0 1 0, ½ ½ ½,
0 0 1, 1 0 1, 1 1 1, 0 1 1
CRYSTALLOGRAPHIC DIRECTIONS

• Defined as line between two points: a vector

• Steps for finding the 3 indices denoting a direction
– Determine the point positions of a beginning point (X1 Y1 Z1)
and a ending point (X2 Y2 Z2) for direction, in terms of unit cell
edges
– Calculate difference between ending and starting point
– Multiply the differences by a common constant to convert them
to the smallest possible integers u, v, w
– The three indices are not separated by commas and are
enclosed in square brackets: [uvw]
– If any of the indices is negative, a bar is placed in top of that
index
COMMON DIRECTIONS
 EXAMPLES: DIRECTIONS
• Draw a [1,-1,0] direction within a cubic unit cell

• Determine the indices for this direction

– Answer: [120]
 CRYSTALLOGRAPHIC PLANES
• Crystallographic planes specified by 3 Miller
indices as (hkl) Z

• Procedure for determining h,k and l:

– If plane passes through origin, translate plane
or choose new origin
– Determine intercepts of planes on each of the
axes in terms of unit cell edge lengths (lattice 1 /2

parameters). Note: if plane has no intercept

to an axis (i.e., it is parallel to that axis), 1 /4

intercept is infinity (½ ¼ ½) Y

– Determine reciprocal of the three intercepts 1 /2

(2 4 2) X
(1 2 1 )

– If necessary, multiply these three numbers by

a common factor which converts all the
reciprocals to small integers (1 2 1)
– The three indices are not separated by
commas and are enclosed in curved
brackets: (hkl) (121)
– If any of the indices is negative, a bar is
placed in top of that index
 THREE IMPORTANT CRYSTAL
PLANES

( 1 0 0) (1 1 0 ) (1 1 1 )
 THREE IMPORTANT CRYSTAL
PLANES
• Parallel planes are equivalent
EXAMPLE: CRYSTAL PLANES
• Construct a (0,-1,1) plane
 FCC & BCC CRYSTAL PLANES
• Consider (110) plane

• Atomic packing different in the two cases

• Family of planes: all planes that are crystallographically equivalent—that is having the same atomic packing, indicated as {hkl}
– For example, {100} includes (100), (010), (001) planes
– {110} includes (110), (101), (011), etc.
 LINEAR & PLANAR DENSITIES
• Linear density (LD) = number of
atoms centered on a direction
vector / length of direction vector
– LD (110) = 2 atoms/(4R) = 1/(2R)
• Planar density (PD) = number of
atoms centered on a plane / area
of plane
– PD (110) = 2 atoms / [(4R)
(2R2)] = 2 atoms / (8R22) =
1/(4R22)
• LD and PD are important
considerations during
deformation and “slip”; planes
tend to slip or slide along planes
with high PD along directions with
high LD
 CRYSTALS AS BUILDING BLOCKS
• Single crystal: when the periodic and repeated
arrangement of atoms is perfect and extends throughout
the entirety of the specimen
• Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives Fig. 8.30(c), Callister 6e.
(Fig. 8.30(c) courtesy
(Courtesy Martin Deakins, of Pratt and Whitney).
GE Superabrasives,
Worthington, OH. Used with
permission.)

• Crystal properties reveal features

of atomic structure.
--Ex: Certain crystal planes in quartz
fracture more easily than others.

(Courtesy P.M. Anderson)

 SINGLE VS POLYCRYSTALS
• Single Crystals E (diagonal) = 273 GPa
Data from Table 3.3,
-Properties vary with Callister 6e.
(Source of data is R.W.
direction: anisotropic. Hertzberg, Deformation
and Fracture Mechanics
-Example: the modulus of Engineering
Materials, 3rd ed., John
of elasticity (E) in BCC iron: Wiley and Sons, 1989.)

E (edge) = 125 GPa

• Polycrystals
-Properties may/may not 200 mm Adapted from Fig.
4.12(b), Callister 6e.
vary with direction. (Fig. 4.12(b) is courtesy
of L.C. Smith and C.
-If grains are randomly Brady, the National
Bureau of Standards,
oriented: isotropic. Washington, DC [now
the National Institute of
(Epoly iron = 210 GPa) Standards and
-If grains are textured, Technology,
Gaithersburg, MD].)
anisotropic.
 AMORPHOUS MATERIALS
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.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.18(b),
Callister 6e.
 SUMMARY
• Atoms may assemble into crystalline,
polycrystalline 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.