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Topic-2: Structure of Crystalline Solids
Materials:- Crystalline and Non-crystalline materials
Atomic Structure and Atomic bonding in solids
(Non-Crystalline)
Crystalline Solid: Crystal structures
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Atomic structure
Every atom consists of a:
Small nucleus composed of protons and neutrons, which is encircled by moving electrons in their
orbitals, specific energy levels
The top most orbital electrons, valence electrons, affect most material properties that are of interest to
engineer.
For example: chemical properties, nature of bonding, size of atom, optical/magnetic/electrical
properties
Atom has:
Atomic number (Z) - is the number of protons per atoms.
Atomic mass (A) - is the sum of the masses of protons and neutrons within the nucleus
Atoms are clustered together by forming bond
Bonds are two types: Primary and Secondary
Primary bonds relatively stronger: Exists in almost all solid materials.
Secondary bonds relatively weaker bonds: Exists in many substances like water along with primary
bonds.
Primary inter-atomic bonds
Ionic Bond: This bond exists between two atoms when transfer of electron(s) results in
one of the atoms to become negative (has an extra electron) and another positive (has
lost an electron)
Covalent Bond: This bond comes into existence if valence electrons are shared between
a pair of atoms, thus acquire stability by saturating the valence configuration.
Covalent bonds are stereospecific i.e. each bond is between a specific pair of
atoms, which share a pair of electrons (of opposite magnetic spins).
Typically, covalent bonds are very strong, and directional in nature.
Metallic Bond: This bond comes into existence if valence electrons are shared between
number of atoms, i.e. arranged positive nucleuses are surrounded by electron pool.
Shared electrons are not specific to a pair of atoms, in contrast to Covalent bond,
i.e. electrons are delocalized.
As shared electrons are delocalized, metallic bonds are nondirectional
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Primary inter-atomic bonds
Type of Bond Properties Examples
Ionic High Melting Point, Brittle, Hard NaCl, MgO
Covalent bond High Melting Point, Hard, Non-conducting C( Diamond), SiO2
Metallic Variable Hardness and Melting Point (depending upon Fe, Mg, Al
strength of metallic bonding), Conducting
Secondary Bond:
Vander Waals Bond:
These bonds involves atomic or molecular dipoles.
Bonds can exists between induced and permanent dipoles (polar molecules).
Type of material Character of bonding Examples
Metal Metallic Fe, steels Al, Cu, Ni
Ceramic and glasses Ionic/ covalent Silica (SiO2)
Polymers Covalent and secondary Polyethylene –(CH2)-
Structure: Crystalline Solid
Atomic Bonding
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Crystal: Lattice + Basis
A crystal consists of a periodic arrangement of the unit cell into a lattice.
Crystals consist of planes of atoms that are spaced a distance d apart,
but can be resolved into many atomic planes, each with a different d spacing.
A lattice is an infinite arrangement of mathematical points in space (3D) or in the
plane (2D) or on a line (1D), in which all points have the same surrounding
Unit cell: The unit cell can contain a single atom or atoms in a fixed
arrangement.
Unit Cell
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The Concept of the Unit Cell
The deconstruction of a large cube into several identical small cubes
Breaking up of a cube into identical rectangular prisms
This geometric solid can be divided into hexagonal pillars
Two ways of dividing hexagonal prisms
8 faces 6 faces (having 8 faces) into solids of only 6
faces :
Slicing along the middle of the long axis
resulting in two pillars with trapezoid
cross sections
Dissecting from the center into three
identical pillars with a rhombic basal face
in which the edges enclose an angle of
120°.
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7 Crystal
system and 14
Bravais Lattice
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Miller indices
A system of notation is required to identify particular direction(s) or plane(s) to characterize the
arrangement of
atoms in a unit cell
Formulas involving Miller indices are very similar to related formulas from analytical geometry –
simple to use
3D indexing in Crystallographic Plane
Draw (100) plane of the cubic crystal Step 1:
Identify the intercepts on the x- , y-
and z- axes.
In this case the intercept on the x-
axis is at x = a ( at the point (a,0,0) ),
but the surface is parallel to the y-
and z-axes - strictly therefore there is
no intercept on these two axes but
we shall consider the intercept to be
at infinity (∞) for the special case
where the plane is parallel to an axis.
The intercepts on the x- , y- and z-
axes are thus a , ∞ , ∞.
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Step 2:
Specify the intercepts in fractional co-ordinates
Co-ordinates are converted to fractional co-ordinates by
dividing by the respective cell-dimension –
for example, a point (x, y, z) in a unit cell of dimensions a x
b x c has fractional co-ordinates of (x/a , y/b , z/c).
In the case of a cubic unit cell each co-ordinate will simply
be divided by the cubic cell constant, a.
This gives Fractional Intercepts = a/a , ∞/a, ∞/a
i.e. 1 , ∞ , ∞.
Step 3:
Take the reciprocals of the fractional intercepts
This final manipulation generates the Miller Indices which (by
convention) should then be specified without being separated
by any commas or other symbols.
The Miller Indices are also enclosed within standard brackets
(….) when one is specifying a unique surface such as that being
considered here.
The reciprocals of 1 and ∞ are 1 and 0 respectively, thus
yielding Miller Indices (100).
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Draw (110) plane of the cubic crystal
Step-1: Intercepts: a , a , ∞
Step-2: Fractional intercepts:
1,1,∞
Step-3: Convert into a smallest
integers in the same ratio
Miller Indices: (110)
Draw (111) plane of the cubic crystal
Intercepts: a , a , a
Fractional intercepts: 1 , 1 , 1
Miller Indices: (111)
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Crystallographic Direction
Direction : Represented
under square bracket []
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• The c-axis is not shown in the figure as r is assumed to lie on the ab plane.
• The components of r along the three axes are: r1 = 2, r2 = 3 and r3 = 0.
• Then the crystal direction denoted by r is written as [230] in the Miller notation, with square brackets
enclosing the indices
• If there is a negative component along a crystal axis such as –2, it is written as 2 and read as bar 2
Planes and Spacing
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Unit cell
It is characterized by:
Type of atom and their radii, R
Cell dimensions [ a and c (for hexagonal structures) (lattice parameter)]
Number of atoms per unit cell, n
Coordination number (CN)– closest neighbors to an atom
Atomic packing factor, APF
Most common unit cells – Face-centered cubic, Body centered cubic and Hexagonal.
Unit Cell n CN a/R APF
Simple Cubic (SC) 1 6 0.52
Body-Centered cubic 2 8 0.68
Face-Centered cubic 4 12 0.74
Hexagonal close Packed 6 12 0.74
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Face-Centered Cubic Crystal
Face-Centered Cubic Crystal
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Hexagonal closed packed crystal structure
Note: Example in given in William D. Callister chapter-3
Hexagonal closed packed crystal structure
Note: Example in given in William D. Callister chapter-3
