Atomic Order in Solids

2ME03 MSM Lecture 5

Shashank P Joshi
Crystal Structure Level
➢We have understood the properties associated with atomic
level structure, the focus was an individual atom or an ion or
a molecule.
➢As we know, there are very large number of atoms or ions or
molecules in a solid, we are interested in their coordination;
not only two, but more than two.
➢At crystal structure level, we evaluate the coordination of
group of atoms/ions/molecules.

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Crystal Structure Level
➢With the help of x-ray diffraction technique, it was realized that in many
materials there is an orderly arrangement of atoms/ molecules; for
example, in metals, atoms are found in regular order, means positioned
with respect to each other in specific pattern throughout.
➢Some of the properties of crystalline solids depend on the crystal
structure of the material, the manner in which atoms, ions, or molecules
are spatially arranged.
➢There is an extremely large number of different crystal structures all
having long-range atomic order; these vary from relatively simple
structures for metals to exceedingly complex ones, as displayed by some
of the ceramic and polymeric materials.

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 X-ray Diffraction
Used to determine
crystal structure

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Crystal Structure Level
➢A crystalline material is one in which the atoms are situated in a
repeating or periodic array over large atomic distances—that is,
long-range order exists, such that upon solidification, the atoms
will position themselves in a repetitive three-dimensional
pattern, in which each atom is bonded to its nearest neighbor
atoms.
➢All metals, many ceramic materials, and certain polymers form
crystalline structures under normal solidification conditions.
➢For those that do not crystallize, this long-range atomic order is
absent; these noncrystalline or amorphous materials
➢Crystals possess a periodicity produces long range order.

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Periodicity (Repetitive) & Identical
Surrounding
NaCl Crystal Structure (FCC)
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Here each Na ion is bonded
with one Cl ion.
But there are large number of
ions, and it is observed that,
NaCl is not molecular.
(Experimental evidence)
Each Na ion is surrounded by
six Cl ions, and each Cl ion is
coordinated with six Na ions.
Cl ions are arranging
themselves in FCC.
It is a group of Na ions and
group of Cl ions in
equilibrium.
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Why atoms arrange them in order?
➢Group of atoms arrange themselves in such a way so that
the arrangement is stable. (Lowest free energy of group.)
➢Implies that the atoms in a group coordinate with each
other, to be stable and are in equilibrium.
➢For example, iron at room temperature is BCC. Each iron
atom coordinates with EIGHT SURROUNDING NEIGHBOURS.

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What is ‘order’? What if complete order is not
present?
Lack of order of any kind leads to higher
free energy, and system is not as stable
as with complete order.

CN - ? CN - ? CN - ?
❖ What if, atom at one of the position is missing/absent?
❖ What if, atom at one of the position is of different type?
✓ Obviously, if all atoms of the group are present, say eight in BCC, in
equilibrium condition, they maintain specific relationships of the lattice
parameter, ‘a’ in cubic systems and angle is 90 degree.
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Cu-Ni System: Cu & Ni are both FCC

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Inferences drawn from the ‘order’
➢Also note that they are arranged in a specific geometric pattern, with
constant lattice parameter and angles.
➢Bravais lattice – 14 space lattices, 7 crystal systems.
➢Why we can measure lattice parameters? Despite of thermal vibrations,
they maintain specific interatomic spacing. From the results of x-ray
diffraction, one can compute atomic radius, lattice parameters.
➢For example, α – iron, which is stable in BCC form at room temperature,
the lattice parameter is 0.2866 nm.
➢A unit cell characterizes the whole crystalline material.
➢The properties of unit cell will be same everywhere.
➢Strength, Density, Plastic deformation, Electrical conductivity are
correlated to crystal structure level.
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 After load removal
F
Elastic strain
And
Elastic stress

a
DISORDERED STR.
F
A crystal structure ε (Permanent)Plastic strain
In equilibrium and Plastic stress
σ
All atoms are positioned
At their lattice positions. σ
Ordered structure
For illustration purpose,
only two corner atoms’
movement has been shown. Shashank P Joshi 12
Crystal Structure and Density Correlation
➢Density = Mass/Volume
➢Consider volume of a unit cell.
✓Information required – type of crystal? (FCC, BCC,..), lattice parameter?
(can be calculated from radius also in cubic system).
➢How much mass per that volume of unit cell?
✓Information required – type of atom? (Atomic mass), Effective number
of atoms per unit cell?
➢So density is correlated to atomic and crystal structure level.
➢Check whether this theoretical calculated density match with
reported value in literature. Analyze the answer.
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Crystal Structure and Electrical Conductivity
➢We have studied earlier that, electrical conductivity is
related to atomic level, number of valence electrons of an
atom which can be delocalized.
➢The delocalized electrons, have wave characteristics as they
move throughout a material. Waves proceed with a
minimum of interruption when traveling through a periodic
structure, i. e. a structure with a pattern that has uniform
reptition.

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Crystal Structure and Electrical Conductivity
➢Any irregularity in the repetitive structure through which the
wave travels deflect the wave.
➢The mean free path – the representative distance electron
can travel in a material.
➢With longer mean free paths, greater drift velocities, are
attained in a given electric field; the higher ratio of drift
velocity to electric field, permits higher charge mobility;
which is directly related to electrical conductivity.

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Crystal Structure and Electrical Conductivity
➢The sequence –
➢mean free path drift velocity mobility conductivity
– will let us anticipate the effect of various structural factors
upon the electrical behaviour of a material.
✓Increased temperature
✓Alloying element – type and amount
✓Deformed lattice due to processing

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Grain structure before wire drawing and
after wire drawing is changing due to wire
drawing process. Within grains the lattice is
also distorted.
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A pure Cu wire – 99.9%
is used for electrical wires.
It is required to reduce the
wire diameter by wire drawing
process, each time the wire is
drawn, its electrical resistance
increases.
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Piezoelectricity

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Piezoelectric Crystals – ‘Centered Crystals’

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 Ultrasonic Probes –
Generates ultrasonic sound
Waves of constant frequency,
which are sent in material,
Receives back and convert into
An electrical signal.

InkJet Printer Head

Applications of Piezoelectric Phenomenon

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Topics to be covered with self-exercise
➢Coordination number – SC, BCC, FCC, HCP, Ionic
coordination – r/R ratio and respective CN, Covalent
coordination
➢Calculate Effective number of atoms for SC, BCC, FCC, HCP.
➢Calculate lattice parameter from atomic radius for SC, BCC,
FCC.
➢Find out examples of materials having BCC, FCC and HCP
crystal structures.

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Topics to be covered with self-exercise
➢Calculate theoretical density of various materials. Find out
value of density reported in literature.
➢Miller indices for planes, directions – Draw yourself the
exercises given in the laboratory session. You should be able
to draw a plane and a direction; given the indices. Same way,
if the plane or direction is given, you should be able to find
out the indices with correct notation. Calculate linear density
for a given direction, planar density for a given plane.

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