CONTENT:

FUNDAMENTAL CONCEPTS
UNITS CELLS
METALLIC CRYSTAL STRUCTURES
The Face-centered Cubic Crystal Structure
The Body-centered Cubic Crystal Structure
The Hexagonal Close-packed Crystal Structure

DENSITY
POLYMORHISM AND ALLOTROPY
CRYSTALOGRAPHIC DIRECTION AND PLANE
LINEAR AND PLANER ATOMIC DENSITIES
 Solid materials may be classified according to the regularity
with which atoms or irons are arranged with respect to one
another
 Crystalline:
– The atoms are situated in a repeating or periodic array over large
atomic distance; long-range order exists (upon solidification),
atoms will position themselves in a repetitive three-dimensional
pattern, each atom bonded to its nearest-neighbor atom
– All metal, many ceramic and certain polymers form crystalline
under normal solidification condition
– For those do not crystalline (noncrystalline or amorphous) –
long-range atomic is absent
 Crystal structure:
– The manner in which atoms, ions
or molecules are spatially arranged
– Atoms / ions are thought of as
being solid spheres having well-
defined diameters – atomic hard
sphere model (figure) in which
spheres representing nearest
neighbor atoms touch one another
– ‘lattice’ – three-dimensional array
of points coinciding with atom
positions
• In describing crystal structures, it is often convenient to
subdivide the structure into small repeat entities called unit
cells.
• Unit cell is chosen to represent the symmetry of the crystal
structure , wherein all the atom positions in the crystal may be
generated by translations of the unit cell integral distance along
each of its edges.
• Unit cell is the basic structural init or building block of the
crystal structure & defines the crystal structure by virtue of its
geometry & the atom positions within.
 The atomic bonding in this group of materials is:
 metallic & nondirectional in nature.
 no restrictions as to the number & position of nearest-neighbor
atoms – lead to relatively large numbers of nearest neighbors &
dense atomic packing for most metallic crystal structures.

 Table1 presents the atomic radii for a number of metals.

 Three relatively simple structure are found for most of the
common metals:
1) Face-Centered Cubic, (FCC)
2) Body-Centered Cubic (BCC), and
3) Hexagonal Close-Packed (HCP)
 Table 1: Atomic Radii and Crystal Structures for 16 Metals.

Metal Crystal Atomic Metal Crystal Atomic

Structur Radius Structur Radius
e (nm) es (nm)

Aluminum FCC 0.1431 Molybdenum BCC 0.1363

Cadmium HCP 0.1490 Nickel FCC 0.1246

Chromium BCC 0.1249 Platinum FCC 0.1387

Cobalt HCP 0.1253 Silver FCC 0.1445

Copper FCC 0.1278 Tantalum BCC 0.1430

Gold FCC 0.1442 Titanium (α) HCP 0.1445

Iron (α) BCC 0.1241 Tungsten BCC 0.1371

Lead FCC 0.1750 Zinc HCP 0.1332

 Had found for many metals
 Unit cell of cubic geometry, with atoms located at each of the
corners & the centers of all the cube faces.

(b)
(a)
 Figure (b)- the atoms centers are
 Figure (a) – hard sphere model for the
represented by small circles to provide a
FCC unit cell,
better perspective of atom positions.
 These sphere or ion cores touch one another across a face
diagonal; the cube edge length a & the atomic radius R are related
through:
a = 2R(2)

Refer to Figure (a):

each corner atom is shared among
eight unit cells
a face-centered atom belongs to only
two, and
One atom located at a center of unit
cell
TOTAL: 4 atoms may assigned to a
given unit cell (a)
 Two other important characteristics of a crystal structure:
1) coordination number, and
2) the atomic packing factor (APF).

 For metals, each atom has the same number of the nearest-neighbor
or touching atoms, which is the coordination number.
 The APF is the fraction of solid sphere volume in a unit cell, assuming
the atomic hard sphere model, or

APF = volume of atom in a unit cell

total unit cell volume

 For FCC:
 The coordination number is 12.
 Atomic packing factor (APF) is 0.74, which the max packing possible for
sphere all having the same diameter.
• Coordination no. = 12
• Length across face-diagonal =
4R = 2. a
• Atom radius, R = (2.a)/4
• Each unit cell consist of =
(6 x ½) + (8 x 1/8) atom = 4 atom/cell

No. of atom/unit cell

Volume/atom
4
4 x  ( 2 a / 4)3
APF  3
a3
Total unit cell volume

• APF for FCC = π/(32) = 0.74 or 74%

 Center and corner atoms touch one another along
cube diagonals, thus unit cell length a and atomic
radius R are related through:
a = 4R/ 3
• Coordination no. = 8
• Length across face-diagonal= 4R = 3.a
R
a
• Atom radius, R = (3.a) / 4
• Each unit cell consist of=
1 + (8 x 1/8) atom = 2 atom/sel
No. of Atom/unit sel Volume/atom
4
2 x  ( 3 a / 4)3
APF  3
a3 Total unit cell volume

• APF for BCC = π(3/8) = 0.68 or 68%

 Top and bottom faces of unit cell consist of six
atoms, single atom in the center and three
additional atoms between the top and bottom
plane
 Each unit cell consist of 6 atoms
 1/6 of each of the 12 atoms at top and bottom
 ½ of 2 atoms at center of top and bottom
 3 midplane interior atoms
 Coordination no: 12
 AFP : 0.74
1) Calculate the volume of an FCC unit cell in terms of the
atomic radius R.
2) Show that the atomic packing factor for the FCC
crystal structure is 0.74.
 A knowledge of the crystal structure of a metallic solid permits
computation of its theoretical density ρ through the relationship:

ρ = nA / VC NA

Where:
n = number of atoms associated with each unit cell
A = atomic weight
VC= volume of the unit cell
NA= Avogadro’s number (6.023 x 1023 atoms/mol)
Question:
Copper has an atomic radius of 0.128 nm (1.28Å), an FCC crystal structure,
and an atomic weight of 63.5 g/mol. Compute its density and compare the
answer with its measured density.

Solution:
Since the crystal structure is FCC, n, the no. of atoms per unit cell is 4.
Furthermore, the atomic weight Acu is given as 63.5 g/mol. The unit cell
volume Vc for FCC is 16R3 2, where R the atomic radius is 0.218 nm.
ρ= nAcu = nAcu
VC NA (16R3 2) NA

= (4 atom/unit cell)(63.5 g/mol)

[162(1.28x 10-8 cm)3/unit cell](6.032 x 1023 atoms/mol)
= 8.89 g/cm3
 Polymorphism – a phenomenon of some metal & nonmetals have
more than one crystal structure.
 In the elemental solids, the condition is often termed allotropy.
 The prevailing crystal structure depends on both:
1) the temperature &
2) the external pressure.
Example:
i. carbon: graphite is a stable polymorph at ambient conditions, whereas
diamond is formed at extremely high pressures.
ii. Iron: Has a BCC crystal structure at room temperature, but changes to
FCC iron at 912°C.

 Most a modification of density and other physical properties will

lead to polymorphic transformation.
 According to unit cell geometry, crystal structure are groups
within the seven crystal system (Figure 1)
 Unit cell geometry is defined in terms of six parameters:
– Three edge lengths a, b and c Lattice parameters
– Three interaxial angles α, β and γ

• The cubic system has the greatest

degree of symmetry, and least
symmetry is display by triclinic system. β α
• FCC and BCC belong to cubic crystal c y
γ a
structure and HCP fall within hexagonal.
b
x
 It is often necessary to be able to specify certain directions and
planes in crystals.
 Many material properties and processes vary with direction in the
crystal.
 Directions and planes are described using three integers - Miller
Indices
 Point position specified in terms of its coordinates as
fractional multiples of the unit cell edge lengths
 Find the Miller indices for the points in the cubic unit cell below:

Note: J is on the left face of the cube, H is on the right face,

K is on the front face and I is on the back face

A :
B :
C :
D :
E :
F :
G :
H :
I :
J :
K :
 Miller indices used to express lattice planes and directions
 x, y, z are the axes (on arbitrarily positioned origin)
 a, b, c are lattice parameters (length of unit cell along a side)
 h, k, l are the Miller indices for directions and planes- expressed as:
– directions: [hkl] and
– planes : (hkl)
 Conventions for naming
 There are NO COMMAS between numbers
 Negative values are expressed with a bar over the number
Example: -2 is expressed 2

• Crystallographic direction: • Crystallographic plane:

– [123] – (123)
– [100] – (100)
– … etc. – … etc.
 Defined as a line between two points, or a vector.
 Methods:
1) Draw vector that pass through the origin of the coordinate system
2) The length of the vector projection on each of the three axes is
determined; these are measured in terms of the unit cell dimensions a, b
and c.
3) Remove fractions by multiplying or divided by a common factor to
reduce them to the smallest integer values
4) Enclose in square brackets [uvw]. The u, v and w integers correspond to
the reduced projection along the x, y and z axes, respectively.

 Negative direction, for example, the [111] direction would have a

component in the –y direction.
[???] =
A: D:
B: E:
C: F:
 Equivalence of directions

 <123> Family of directions

 [123], [213], [312], [132], [231], [321]
 only in a cubic crystal
 In the cubic system directions having the same indices regardless
of order or sign are equivalent.
 (hkl) Crystallographic plane
 {hkl} Family of crystallographic planes
 e.g. (hkl), (lhk), (hlk) … etc.

 In the cubic system planes having the same indices regardless

of order or sign are equivalent
 Hexagonal crystals can be expressed in a four index system
(uvtw)
 Can be converted to a three index system using formulas
 Method
1) If the plane passes through the
origin, select an equivalent plane
or move the origin
2) Determine the intersection of
the plane with the axes in terms
of a, b, and c
3) Take the reciprocal (1/∞ = 0)
4) Convert to smallest integers
(optional)
5) Enclose by parentheses
 Planes and their negatives are  In the cubic system, a plane and
equivalent a direction with the same
indices are orthogonal
Linear Density
 Number of atoms per length whose centers lie on the direction vector for
a specific crystallographic direction.

LD = No. of atoms centered on a direction vector

length of direction vector

Planar Density
 Number of atoms per unit area that are centered on a particular
crystallographic plane.

PD = No. of atoms centered on a plane

area of plane
1. Calculate the linear density of the [100] direction for BCC
2. Calculate the planar density of the (100) plane for FCC
Why do we care?
 Properties, in general, depend on linear and planar density.
Examples:
 Speed of sound along directions
 Slip (deformation in metals) depends on linear and planar
density
 Slip occurs on planes that have the greatest density of atoms
in direction with highest density (we would say along closest
packed directions on the closest packed planes)