Crystallography
1
Snow flakes
Metal Crystals
Periodicity of atoms
Atoms/crystals representation
➢Crystallography is that branch of science in
which the internal structure of crystals, their
properties, external or internal symmetries of
crystals are studied.
➢Various terms associated with crystallography
are:
▪ Crystal is a solid whose constituent atoms or
molecules are arranged in a systematic
geometric pattern
▪ Structure implies the arrangement and
disposition of atoms within a crystal
▪ The atoms arrange themselves in distinct pattern in
space called a space lattice
▪ Unit cell is the smallest group of atoms possessing
the symmetry of the crystal
▪ The layers of atoms or the planes along which atoms
are arranged are known as atomic or
crystallographic planes
▪ Characteristic intercepts and interfacial angles of
crystal constitute the lattice parameters of a cell
▪ Miller indices is a system of notation for
designating crystallographic planes and
directions
▪ Atomic Packing Factor is the ratio of volume of
atoms per unit cell to the total volume occupied
by the unit cell
▪ Coordinate no. is the number of nearest atoms
directly surrounding a given atom in a crystal
i.e., nearest neighbours to an atom in a crystal
Important planes of Hexagonal Crystals
Crystal Systems
Unit cell: basic building block of the crystal
7 crystal systems of varying
symmetry are known
These systems are built by
changing the lattice parameters:
a, b, and c are the characteristic
intercepts
, , and are interfacial angles
Fig. 3.4, Callister 7e.
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15
Bravais Lattices
Parameter that characterises the crystal structure
• Lattice parameters
• Atoms per unit cell
• Coordination number- no. of nearest neighbouring
atoms
• Atomic packing factor =
(Volume occupied by atoms in the unit cell)/
(Volume of unit cell)
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Atoms in unit cell
1
1/2
1/4
1/8
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Copyright © Houghton Mifflin Company. All rights reserved. 16a–18
Simple Cubic Structure (SC)
• Rare due to low packing density (only Po – Polonium
-- has this structure)
• Close-packed directions are cube edges.
• Coordination No. = 6
(# nearest neighbors) for each atom as
seen
(Courtesy P.M. Anderson) 19
Atomic Packing Factor (APF)
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
a 4
unit cell 1 p (0.5a) 3
R=0.5a 3
APF =
a3 volume
close-packed directions
unit cell
contains (8 x 1/8) =
1 atom/unit cell Here: a = Rat*2
Where Rat is the atomic radius 20
Adapted from Fig. 3.23, Callister 7e.
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Body Centered Cubic Structure (BCC)
• Atoms touch each other along cube diagonals within a unit cell.
--Note: All atoms are identical; the center atom is shaded differently only for ease of
viewing.
ex: Cr, W, Fe (), Tantalum, Molybdenum
Adapted from Fig. 3.2,
Callister 7e.
• Coordination # = 8
2 atoms/unit cell: (1 center) + (8 corners x 1/8)
(Courtesy P.M. Anderson)
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Atomic Packing Factor: BCC
3a
2a
Close-packed directions:
R
a length = 4R = 3 a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
volume
Adapted from
Fig. 3.2(a), Callister 7e.
a3
unit cell
• APF for a body-centered cubic structure = 0.68 23
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Face Centered Cubic Structure (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded differently only for ease
of viewing.
ex: Al, Cu, Au, Pb, Ni, Pt, Ag
• Coordination # = 12
Adapted from Fig. 3.1, Callister 7e.
(Courtesy P.M. Anderson) 4 atoms/unit cell: (6 face x ½) + (8 corners x 1/8)
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Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
The maximum achievable APF!
Close-packed directions:
2a length = 4R = 2 a
(a = 22*R)
Unit cell contains:
6 x 1/2 + 8 x 1/8
a = 4 atoms/unit cell
Adapted from
atoms volume
Fig. 3.1(a),
4
Callister 7e.
unit cell 4 p ( 2a/4) 3
3 atom
APF =
volume
a3
unit cell 26
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Hexagonal close packed (HCP)
• A hexagonal close packed structure has
– One atom at each corner of the hexagon
– One atom at the centre of two hexagonal faces (Basal
planes)
– One atom at the centre of the line connecting the
perpendiculars in case of three rhombuses which
combine and form the hexagonal close packed structure
• Atomic Packing Factor = 0.74
• Eg.: Zn, Cd, Be, Mg
Hexagonal close packed (HCP)
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Properties of crystalline solids:
➢These solids have a particular three dimensional geometrical
structure.
➢The arrangement order of the ions in crystalline solids is of long
order.
➢The strength of all the bonds between different ions, molecules and
atoms is equal.
➢Melting point of crystalline solids is extremely sharp. Mainly the
reason is that the heating breaks the bonds at the same time.
➢The physical properties like thermal conductivity, electrical
conductivity, refractive index and mechanical strength of crystalline
solids are different along different directions.
➢These solids are the most stable solids as compared to other solids.
Properties of Amorphous solids:
➢The strength of different bonds is different in amorphous solids.
➢There is no regularity in the external structure of amorphous solids.
➢On the other hand, amorphous solids don’t have sharp melting point.
This is due to the variable strength of bonds present between the
molecules, ions or atoms. So, bonds having low strength on heating
break at once. But the strong bonds take some time to break. This is the
reason that the amorphous solids don’t have sharp melting points.
➢Amorphous solids are isotropic in nature. Isotropic means that in all
the directions their physical properties will remain same.
Miller Indices
➢Miller indices is a system of notation
for designating crystallographic planes
and directions of planes
Miller indices of a direction
➢ A crystallographic direction is defined as a line or
vector between two points. Following are the steps
for determination of the Miller indices of a direction
1. Determinate the co-ordinates of two points that lie on
the direction, usually a right handed coordinate system
2. Subtract the co-ordinates of tail point from those of the
head point and express the same in terms of the unit
cell dimensions
3. Multiply or divide these numbers by a common factor to
reduce them to the smallest integers
4. The three indices are enclosed in square brackets as
[uvw]. A negative integer is represented with a bar over
the number
Crystallographic Directions
Ex 1: 1, 0, ½ & 0,0,0 => (1,0, ½ ) – (0, 0, 0) => 1,0, ½ => 2,0,1
=> [ 201]
Ex 2:(-1, 1, 1) & (0,0,0) => (-1, 1, 1) – (0, 0, 0) => -1, 1, 1
=> [111 ] where ‘overbar’ represents a
negative index
➢Points to be noted about the use of miller
indices for direction
▪ As the directions are vectors, a direction and its
negative are not identical. The directions [110] & [1
1 0] represent the same line but opposite directions
▪ A direction and its multiple are identical; [120] &
[240] represent same direction
▪ In any crystal system, there are certain groups of
directions which are equivalent and are called family
of directions. In cubic system corresponding to [100]
direction a family of equivalent directions are
obtained by interchanging the positions and signs of
indices. The index when enclosed in angle brackets
represent a family.
<100> = [100], [010], [001], [100], [010], [001]
Miller indices of planes
➢Procedure for determining miller indices of planes
1. If the plane passes through the origin of co-ordinate
system, the origin must be moved to another corner
of unit cell
2. Identify the points at which the plane intercepts the
x,y,z axes and express the intercepts in terms of the
lattice parameters
3. Take reciprocals of these numbers. Intercept for a
plane parallel to an axis to be taken as infinity with
reciprocal equal to zero
4. Change these numbers to a set of smallest integers
by multiplication or division by a common factor
5. Enclose the integer indices within parentheses (hkl)
Crystallographic Planes z
example a b c
1. Intercepts 1 1 c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2 c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (200) a b
x
Crystallographic Planes
z
example a b c
c
1. Intercepts 1/2 1 3/4 •
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 •
•
y
3. Reduction 6 3 4 a b
4. Miller Indices (634) x
➢ Important aspects
▪ Planes and their negatives are identical; (010) = (0 ̅10)
i.e a plane located at the same distance on the other
side of origin
▪ Planes and their multiples are not identical
Family of planes {110}
▪ In cubic system a plane and a direction having the
same indices are perpendicular to each other. Hence
the direction [110] is perpendicular to the plane (110)
in a cubic unit cell.
▪ Parallel planes have the same Miller indices. Distance
between two adjacent parallel planes with same
Miller index (hkl) is called interplanar spacing.
Interplanar spacing in cubic crystals is given by
d=
Family of Planes {hkl}
Ex: {100} = (100), (010), (001), (100), (010), (001)
Miller Bravais Indices
➢Planes and directions in hexagonal crystals are
defined in terms of indices containing four digits
instead of three. Theses are known as Miller
Bravais Indices
➢The four indices are designated as (h k i l) such
that h+k=-i
Deformation of Metals
➢ Deformation – change in shape that take place in a material
when subjected to an external force or load.
➢ Elastic (temporary) and plastic (permanent) deformation.
➢ Both take place due to adjustments or displacement in
atomic arrangement.
➢ Applied load may be tensile, compressive or shear
(constant or fluctuating)
➢ Application time – fraction of second or a period of years
➢ Environmental factors- temperature or corrosive
atmosphere
Elastic deformation
➢ When a material is subjected to an applied force, atoms within the
crystal are displaced from their normal positions of equilibrium -
deformation.
➢ This displacement will be just enough to develop attractive forces
between the atoms to balance the applied load.
➢ Elastic deformation in a solid bar (loaded axially in tension)
➢ Elastic deformation – Displacement of atoms is by small amount –
removal of load allows atoms to return to their normal equilibrium
positions – ie, REVERSIBLE
➢ mn elongates and pq contracts
➢ Poisson effect
➢ As the applied load increases and atoms are displaced
further apart – end of elastic range
➢ Deformation is no longer a simple separation of atoms
– inelastic
➢ Two possible ways by which elastic stage ends:
▪ by yielding
▪ by fracture
▪ BRITTLE –elastic range followed by fracture
Anelastic and Viscoelastic Behaviour
➢ Elastic strain disappears as the applied load is removed.
➢ When a metal is strained plastically and when load is released
elastic strain will recover immediately.
➢ However the strain remaining is not completely plastic strain
➢ Depending upon the metal and the temperature a small
amount of plastic strain will disappear with time.
➢ This time dependent elastic behaviour is called anelasticity
(very small in metals; neglected)
➢ A similar time dependent behaviour exhibited by some polymeric
materials, wood and human tissue is called viscoelasticity
➢ It is the property of materials that exhibit both viscous and elastic
characteristics.
➢ Elasticity is the result of stretching of atomic bonds along
crystallographic planes in an ordered solid.
➢ Viscosity is the result of the diffusion of atoms or molecules inside an
amorphous material
➢ Viscoelastic materials have elements of both these properties and
exhibit time dependent strain…
Plastic Deformation
➢ Due to yielding, some of the atoms move to new equilibrium
positions
➢ Atoms form new bonds in their new positions; hence material is not
weakened and do not return to original positions
➢ Thus the deformation is inelastic or irrecoverable
➢ Such a deformation is permanent, known as plastic deformation.
➢ Two common mechanisms:
➢ by Slip
➢ by Twinning…
Plastic Deformation by Slip
➢ Metals are significantly weaker in shear
➢ Under the influence of a shear force atoms move
relative to each other on certain planes from one
position of equilibrium to another causing a permanent
deformation
➢ Some atoms slip past the other atoms on a certain
plane in a certain direction. This process is called slip
➢ SLIP PLANE: the plane on which slip takes place
➢ SLIP DIRECTION: directions along which atoms move
➢ Slip system: set of favoured plane and direction
Commonly observed slip systems in Metals
Crystal Structure Slip Plane Slip Direction
FCC {111} <110>
BCC {110} <111>
HCP {0001} < 1 1 ̅2 0 >
Schmid’s law
Shear Force, Fr = F cos α
Area of slip plane, A = AO
COS β
Resolved shear stress, r = Fr
A
= F cos α cos β
A0
r = σ cos α cos β ( Schmid’s Law)
F/A0 = σ , the normal stress applied to the bar
Plastic Deformation by Twinning
Plastic Deformation by Twinning
➢ In certain materials, when a shear stress is applied, planes of
atoms in the lattice move parallel to a specific plane so that the
lattice is divided into two symmetrical parts which are
differently oriented. This phenomenon is known as Twinning
➢ Twinning plane: the planes parallel to which atomic movement
has taken place
➢ Twinned region: differently oriented region within the crystal
and the twinning planes
➢ Twinning is produced suddenly and is accompanied with sound
➢ In both slip and twinning, lattice is sheared
➢ In slip, shear is uniformly distributed over a volume rather than
localised on a discrete no of slip planes
➢ Twinning – atoms move only a fraction of interatomic distance
relative to each other
➢ The amount of movement of each plane of atoms in the twinned
region is proportional to its distance from the twinning plane –
Mirror image
➢ Twinning is common in HCP crystals.
➢ During twinning the lattice over the twinned regions may get
favourably oriented for slip w.r.t the applied load.
➢ Thus under certain conditions a twinned metal can be more easily
deformed by slip
Brittleness of BCC, HCP and ductility of FCC
➢ When stressed some materials undergo extensive plastic
deformation – Ductile
➢ Some break up suddenly with very less or no plastic
deformation – Brittle
➢ In crystalline materials dominant mode of plastic deformation is
slip – dependant on available no: of slip systems
➢ Slip occurs easily on planes and in directions of maximum
atomic density – easy slip systems
➢ In FCC, { 1 1 1 } and < 1 1 0 > have max: atomic density – 12
easy slip systems available
➢ Atleast one slip system oriented in a favourable position for
slip to take place
➢ Hence slip and thereby plastic deformation is initiated easily
in FCC crystals
➢ Materials having FCC structure are therefore ductile in nature
➢ BCC crystals also have 12 easy slip systems with { 1 1 0 } and
<111>
➢ However the { 1 1 0 } planes of BCC have lesser atomic
density compared to the { 1 1 1 } planes of FCC
➢ Therefore stress required is high in BCC
➢ So BCC materials are less ductile (plastic) compared to FCC
➢ In HCP, basal planes { 0 0 0 1 } and < 1 1 ̅ 2 0 > have
maximum atomic density
➢ Only 3 easy slip systems are available in HCP
➢ Hence HCP materials are normally brittle
➢ “Less common slip systems” are also available in these
crystals
➢ Become operative at higher stresses or at higher
temperatures.
Correlation of slip system with slip in metals
➢ The value of critical stress varies from material to material depending upon the
strength of interatomic bond
➢ Within a material the value varies with the slip system depending upon the atomic
density on the slip plane and in the slip direction
➢ Hence for a given material critical stress values are different for different slip
systems
r =σ cos α cos β
value of r depends on:
value of applied stress, σ
The angles α and β
➢ For a given direction of the applied stress some slip systems will be
favourably oriented for slip to be initiated
➢ On such a plane slip will take place when the value of resolved shear stress
equals the value of critical resolved shear stress for that slip system
➢ As applied stress is increased from zero deformation will be initiated on
that slip plane and along that slip direction for which resolved shear stress
is maximum and so reaches critical value first.
➢ Thus it is seen that slip and thereby plastic deformation within crystal
structures is dependent on type of slip systems and their orientation with
the direction of applied stress
• Radius ratio
𝑟𝑐
•
𝑟𝑎
• 𝑟𝑐 = radius of cation
• 𝑟�𝑎 = radius of anion