Metallic structure

Objectives
Understand how metal/alloy
structure is formed & relates to
theirs properties?
Outline
 Atomic bonding

 Structure of metals

 Development of grain
structure
Atomic bonding

 All true solids show a crystal structure

which has a definite geometric
arrangement of atoms or molecules.
 Some materials such as glass do not
have a regular arrangement of molecules
and are not true solids but rather super-
cooled liquids.
Atomic bonding
 Question ?
What holds the atoms or
molecules of solids together?

 There are four possible types of bonds:

 i. ionic bond
 ii. Covalent or homopolar bond
 iii. Metallic bond
 iv. Van der Waals forces
Ionic bond
The bond formed by the complete transfer of
electrons from electropositive atoms to more
electronegative atom is called ionic or
electrovalent.
Covalent bond
The bond formed by the
sharing of one, two, or three
electron from each element is
single covalent, double
covalent and triple covalent
bond respectively.
Metallic bond
 When a complete outer shell cannot be formed by
either electron transfer or electron sharing than it
is possible to have a bond known as metallic
bond.
 A metallic bond is the electrostatic force of
attraction that the neighbour positive metallic ions
have for the free (delocalized) electrons.
 The most commonly accepted theory for metallic
bonding is called “electron sea model”
Metallic bond
The highly mobile free electrons account for the
high electrical and thermal conductivity values in
metals.
 Van der Waals Forces
 London Forces called van der Waals forces, are
weak interactions.
 According to the principle of probability, electrons
are not distributed symmetrically around the
nucleus. But they concentrate on one side. Due to
this, molecule becomes a temporary dipole.
 Partial positive and partial negative charges are
developed. Partial negative end of one molecule
attracts the partial positive end of the adjacent
molecule, and a weak interaction is produced.
 The forces are important in non-polar compounds &
exist in compounds having low boiling point, melting
point etc, e.g., inert gases.
Structure of materials
 The physical structure of solid materials depends on the
 arrangement of the atoms, ions or molecules and the
 bonding forces between them.

 Crystalline materials have regular geometrical shape in

which atoms have characteristic regular and repetitive
three dimensional arrangement
 Examples of crystalline materials are metals, alloys
and some ceramic materials.
Classification of Materials-Based on Structure
and Atomic Arrangements

 Crystalline material is a material comprised of one or

many crystals. In each crystal, atoms or ions show a
long-range periodic arrangement.
 Amorphous material is a material whose structure lacks
crystalline periodicity; that is, the pattern of its constituent atoms
or molecules doesn’t repeat periodicity in 3-D.
 Single crystal is a crystalline material that is made of
only one crystal (there are no grain boundaries).
 Grains are the crystals in a polycrystalline material.
 Polycrystalline material is a material comprised of
many crystals (as opposed to a single-crystal material
that has only one crystal).
 Grain boundaries are regions between grains of a
polycrystalline material.
 Lattice, Unit Cells, and Crystal
Structures
 Lattice - A collection of points that divide space into
smaller equally sized segments.
 Basis - A group of atoms associated with a lattice point.
 Unit cell - A subdivision of the lattice that retains the
overall characteristics of the entire lattice.

 Packing factor - The fraction of space in a unit cell

occupied by atoms.

 Atomic radius - The apparent radius of an atom, typically

calculated from the dimensions of the unit cell.
Figure: (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.)
Figure: Summary/Classification of materials based on the type
of atomic order and structure.
Space lattice
 Metallic atoms, on solidification, arrange
themselves in a regular three dimensional pattern.
 The three dimensional network of imaginary lines
connecting atoms is called space lattice,
 Three dimensional lattice indicates the external
shapes of crystal.
 Unit cell
 The smallest unit having the
full symmetry of the crystal is
called the unit cell.
 The specific unit cells for each
metal is defined by its
parameters which are
 the edges of the unit cell a, b,
c (called axial lengths) and
 the angles α (between b & c),
β (between a & c) and 
(between a & b) are called
interaxial angles.
Crystal Structures of Metals
 Metals are characterized by the
 metallic bonds and
 possess the distinguishing characteristics of
 Crystalline structure
 good electrical and thermal conductivity,
 luster,
 the ability to be plastically deformed to a fair degree without
fracturing, and
 a relativity high specific gravity (density) compared to non-
metals.
 strength
 Crystal Structures of Metals
 When metals solidify, the atoms arrange
themselves in a geometric lattice.
 Many metals exist in only one crystal structure or
lattice forms.
 Some metals can exist in solid state in two or more
lattice forms. These metals are said to be allotropic
or polymorphic (poly means “more than one”;
morph means “structure”), and
 The change from the one lattice to another is called
allotropic transformation. The most notable example
of such a metal is iron.
Seven Crystal Systems

 Cubic
 Tetragonal
 Hexagonal
 Orthorhombic
 Rhombohedral
 Monoclinic
 Triclinic
 Figure: Metals exist
in one of the 14
crystal structures at
room temperature

(c) 2003 Brooks/Cole Publishing / Thomson Learning™

 Lattice Parameters & Their Usage =
Dimensions, Angles >>>
Size/ Shape

Figure:
Definition of
the Lattice
Parameters
and their use in
cubic,
orthorhombic,
and hexagonal
crystal systems.

(c) 2003 Brooks/Cole Publishing / Thomson Learning™

TABLE: Characteristics of the seven crystal system
Crystal Structure
 The Crystal Structure of Metals
 3 basic patterns of atomic arrangement in metal:

Body-centered cubic (bcc) Face-centered cubic (fcc) Hexagonal close packed (hcp)
 Crystal Structure
 Most commercially important metals solidify into
one of the three lattice types:
 Examples
 Body - centered cubic (BCC): e.g. Cr, Fe, Mn.

 Face-centered cubic (FCC): e.g. Ag, Au, Pd, Al,

Ca, Cu, Ni
 Hexagonal closed - pack (HCP): e.g. Ti, Zn, Mg,
Cd, Zr

a unit cell
 Body Centered Cubic (BCC) Crystal Structure

 The unit cell for BCC

consists of a sphere
(atom) at the centre of
cube with 8 other spheres
at the corners of the cube
& touching the central
sphere.
 BCC has 2 atoms per unit
cell. 2 atoms/unit cell: 1 center + 8 corners x 1/8
 Figure: (a)
Illustration
showing sharing of
face and corner
atoms. (b) The
models for simple
cubic (SC), body
centered cubic
(BCC), and face-
centered cubic
(FCC) unit cells,
assuming only one
atom per lattice
point.

(c) 2003 Brooks/Cole Publishing / Thomson Learning™

Body Centered Cubic (BCC) Crystal Structure

 If the atoms in the BCC unit cell are considered to

be spherical, an atomic packing factor (APF) can
be calculated by using the following equation:

Atomic packing factor (APF) = Volume of atoms in

unit cell / volume
of unit cell
BCC Unit Cell

atoms
4 volume
unit cell 2 p ( 3 a/4 ) 3
3 atom
APF =
volume
a3
unit cell
 BCC
•APF for the BCC = 68, i.e. 68 percent of the volume of BCC
unit cell is occupied by atoms and the remaining 32 percent is
empty space.
•Therefore packing is not so close as compared to FCC or
HCP.
•Many metals such as iron, Chromium, tungsten, molybdenum
and vanadium have the BCC crystal structure at room temp.
• Compared to materials with other structures, BCC metals
tend to be high strength.
Face-centered-cubic (FCC) crystal structure
 In FCC, there is one lattice point at each corner of the
cube and one at the centre of each cube face.
 FCC has 4 atoms per unit cell.
 The atoms in the FCC crystal structure are packed as
closed together as possible.
4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8
FCC Unit Cell
Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF

2a
Close-packed directions:
length = 4R = 2a

atoms
4 volume
unit cell 4 p ( 2 a/4 ) 3
3 atom
APF =
volume
a3
unit cell
34
 FCC
 The APF for the FCC is 0.74 which is greater than
the 0.68 factor for the BCC structure.
 Plastic deformation of metallic crystals generally
occur by slipping of closed packed planes over each
other.
 FCC is the preferred structure for many of the
engineering metals and tend to provide the
exceptionally high ductility that is the characteristic
of Al, Cu, Pb, Ni, and Fe (at elevated).
 Hexagonal close – packed (HCP)
crystal structure
A stacking sequence of any two alternating layers
results in a structure known as Hexagonal close –
packed (HCP), where the individual close-packed
planes can be clearly identified.
Hexagonal close – packed (HCP) crystal
structure
 The APF of the HCP crystal structure is 0.74,
the same as for the FCC.
 Metals having HCP structures e.g., Mg and
Zn tend to
 have poor ductility,
 fail in brittle manner, and
 often require special processing procedure.
TABLE: Crystal structure characteristics of some metals

6
 of Crystalline Materials

Atomic weight and atomic radius of many elements can be found

in the tables of some textbook/reference book
 Allotropic or Polymorphic
Transformations

 Allotropy - The characteristic of an element being able to

exist in more than one crystal structure, depending on
temperature and pressure.
 Polymorphism - Compounds exhibiting more than one
type of crystal structure.
 Determining the Number of Lattice Points
in Cubic Crystal Systems

Determine the number of lattice points per cell in the cubic

crystal systems. If there is only one atom located at each
lattice point, calculate the number of atoms per unit cell.
Example: SOLUTION
In the SC unit cell: lattice point / unit cell = (8 corners)1/8 = 1
In BCC unit cells: lattice point / unit cell
= (8 corners)1/8 + (1 center)(1) = 2
In FCC unit cells: lattice point / unit cell
= (8 corners)1/8 + (6 faces)(1/2) = 4
The number of atoms per unit cell would be 1, 2, and 4, for the
simple cubic, body-centered cubic, and face-centered cubic,
unit cells, respectively.
 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™
Figure 3.14 The relationships between the atomic radius and
the Lattice parameter in cubic systems (for Example 3.2).
Example: SOLUTION

Referring to Figure 3.14, 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
4r
a0 
3
In FCC structures, atoms touch along the face diagonal
of the cube. There are four atomic radii along this
length—two radii from the face-centered atom and one
radius from each corner, so:
4r
a0 
2
 Calculating the Packing Factor

Calculate the packing factor for the FCC cell.

Example: SOLUTION
In a FCC cell, there are four lattice points per cell; if there is
one atom per lattice point, there are also four atoms per cell.
The volume of one atom is 4πr3/3 and the volume of the unit
3
cell is a 0. 4 3
(4 atoms/cell )( pr )
Packing Factor  3
3
a0
Since, for FCC unit cells, a 0  4r/ 2
4 3
(4)( pr )
3 p
Packing Factor  3
  0.74
( 4r / 2 ) 18
 Determining the Density of BCC Iron

Determine the density of BCC iron, which has a lattice

parameter of 0.2866 nm.
Example: SOLUTION
Atoms/cell = 2, a0 = 0.2866 nm = 2.866  10-8 cm
Atomic mass = 55.847 g/mol
3
Volume of unit cell = a0= (2.866  10-8 cm)3 = 23.54  10-24
cm3/cell
Avogadro’s number NA = 6.02  1023 atoms/mol
(number of atoms/cell )(atomic mass of iron)
Density  
(volume of unit cell)(Avog adro' s number)
(2)(55.847)
   7.882 g / cm 3

(23.54  10 24 )(6.02  1023 )