Metallic bonding

• Metallic bonding is the force of attraction

between valence electrons and the metal atoms.
• It is the sharing of many detached electrons
between many positive ions, where the
electrons act as a "glue" giving the substance a
definite structure.
• It is unlike covalent or ionic bonding
 Metallic bonding
• Metallic bonding accounts for many
physical properties of metals, such as
strength, ductility, thermal and
electrical resistivity and conductivity
and lustre.
 Crystallography
• The word "crystallography" is derived
from the Greek words crystallon = cold
drop / frozen drop, with its meaning
extending to all solids with some degree
of transparency, and
• crystallon = cold drop / frozen drop +
grapho = write.
 Crystallography
• Crystallography is the experimental
science of determining the
arrangement of atoms in solids.
 Crystallography
• Mostly, materials do not occur in a
single crystalline, but poly-crystalline
form, such that the
powder diffraction method plays a
most important role in structural
determination.
 Introduction to
Crystal Structures
 crystal structure
crystal structure
 crystal lattice
• The lattice constant [or lattice parameter] refers
to the constant distance between unit cells in a
crystal lattice.
• Lattices in three dimensions generally have
three lattice constants, referred to as a, b, and c.
• However, in the special case of cubic crystal
structures, all of the constants are equal and we
only refer to a.
• Similarly, in hexagonal crystal structures, the a
and b constants are equal, and we only refer to
the a and c constants.
 Crystallography
• Crystallography is a tool that is often
employed by materials scientists.
• In single crystals, the effects of the
crystalline arrangement of atoms is
often easy to see microscopically,
because the natural shapes of crystals
reflect the atomic structure.
 Space LaTTICE
A geometric arrangement of the points in space at which
the atoms, molecules, or ions of a crystal occur. Also called
space lattice.
 Metallic Crystals

• tend to be densely packed.

• have several reasons for dense packing:
-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.

3
 Metallic Crystal Structures
• The atoms in most simple metals are
arranged in one of the configurations below
• Simple Cubic (sc) - Po (alpha - polonium is one of the few known simple
cubic lattices )
• Body-Centered Cubic (bcc) – Ba, Cs, Cr
• Face-Centered Cubic (fcc) – Cu, Ag,
• Hexagonal Close-Packed (hcp) – Zn, Co, cd
• Nearest-neighbors atoms “touch” in all of
these cases.
Characteristics of Selected Elements at 20C
Crystal Atomic radius
Element Symbol Structure (nm)
Aluminum Al FCC 0.143
Argon Ar ------ ------
Barium Ba BCC 0.217
Beryllium Be HCP 0.114
Boron B Rhomb ------
Bromine Br ------ ------
Cadmium Cd HCP 0.149
Calcium Ca FCC 0.197
Carbon C Hex 0.071
Cesium Cs BCC 0.265
Chlorine Cl ------ ------
Chromium Cr BCC 0.125
Cobalt Co HCP 0.125
Copper Cu FCC 0.128
Flourine F ------ ------
Gallium Ga Ortho. 0.122
Germanium Ge Dia. cubic 0.122
Gold Au FCC 0.144
Helium He ------ ------
Hydrogen H ------ ------ 12
 SIMPLE CUBIC STRUCTURE (SC)
• Rare due to poor packing
• Close-packed directions are cube edges.
• Coordination # = 6
(# nearest neighbors)

4
Simple cubic
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.
 Face Centered Cubic (FCC)
• Atoms are arranged at the corners and center
of each cube face of the cell.
– Atoms are assumed to touch along face diagonals
 Hexagonal Close-Packed Structure (hcp)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

B sites Middle layer

A sites Bottom layer

• Coordination # = 12 Note: this structure is NOT cubic
• APF = 0.74

10
 ATOMIC PACKING FACTOR

Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres
 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 (mass/ volume) can then be
calculated using the
crystal structure of metallic solid material.
 Miller indices
• Miller Indices are a symbolic vector
representation for the orientation of
an atomic plane in a crystal lattice and
are defined as the reciprocals of the
fractional intercepts which the plane
makes with the crystallographic axes.
DETERMINATION OF ‘MILLER INDICES’

• Step 1:The intercepts are 2,3 and 2 on the three axes.

• Step 2:The reciprocals are 1/2, 1/3 and 1/2.

• Step 3:The least common denominator is ‘6’.

• Multiplying each reciprocal by lcm,
we get, 3,2 and 3.

• Step 4:Hence Miller indices for the plane ABC is

(3 2 3)
Miller indices
 Crystallographic Directions
• Cubic systems
– directions are named based upon the projection
of a vector from the origin of the crystal to
another point in the cell.
• Conventionally, a right hand Cartesian
coordinate system is used.
– The chosen origin is arbitrary, but is always
selected for the easiest solution to the problem.
 Specifying Directions in a
(cubic) Crystal
• Choose a right-handed coordinate system
• Pick an origin for your set of axes
– the x-axis is the vector (100)
– the y-axis is the vector (010)
– the z-axis is the vector (001)
• Any direction in the crystal can be defined
using the basis above.
 type: <100>
Equivalent directions:
[100],[010],[001]
 ype: <110>
Equivalent directions:
[110], [011], [101],
[-1-10], [0-1-1], [-10-1],
[-110], [0-11], [-101],
[1-10], [01-1], [10-1]
 type: <111>
Equivalent directions:
[111], [-111], [1-11], [11-1]
Important directions in 3D represented by Miller Indices (cubic lattice)

[001] [011] Memorize

these
Z
[101]

Y [010]
Body diagonal
[100]
[110] [111]
X [110]
Face diagonal

Procedure as before:
• (Coordinates of the final point  coordinates of the initial point)
• Reduce to smallest integer values
 REFERENCES
• https://en.wikipedia.org/wiki/Crystal_structur
e
• https://web.iit.edu/sites/web/files/departmen
ts/academic.../Crystal_Structures.pdf
• https://study.com/academy/.../crystalline-
structu
• https://
www.youtube.com/watch?v=BjVTdZ_htu8re-
definition-structure-bonding.htm
www.geocities.jp/ohba_lab_ob_page/Structur