Introduction and Crystallography
Introduction and Crystallography
I would like to express my sincere gratitude to Dr. Bijit Choudhuri, Faculty, NIT Silchar, sir
for his class presentation slides and NPTEL lecture series on “Introduction to Materials Science
and Engineering” by Prof. Rajesh Prasad which forms the majority of the contents of the 1st
chapter. Also minor contribution from the reference books of our institute syllabus and some
random internet sources are incorporated.
Ref. Ha et al, “Wearable and flexible sensors for user-interactive health-monitoring devices” J. Mater. Chem. B, 2018, 6, 4043
Engineering
requirements
Impact Thermal
Valency
Strength Resistance
Corrosion Thermal
Acidity
Resistance Diffusivity
Density alkalinity
Materials
Advanced
Metals Ceramics Polymers Composites
materials
Semiconductors
Biomaterials
Smart Materials
Nanomaterials
Materials in this group are composed of one or more metallic elements and often also
nonmetallic elements (e.g., carbon, nitrogen, and oxygen) in relatively small amounts.
e.g., iron, aluminum, copper, titanium, gold, and nickel. Atoms in metals and their
alloys are arranged in a very orderly manner and in comparison to the ceramics and
polymers, are relatively dense. Metallic materials have large numbers of nonlocalized
electrons; that is, these electrons are not bound to particular atoms. Many properties of
metals are directly attributable to these electrons. For example, metals are extremely
good conductors of electricity and heat, and are not transparent to visible light; a
polished metal surface has a lustrous appearance. In addition, some of the metals (i.e.,
Fe, Co, and Ni) have desirable magnetic properties. metal alloy refers to a metallic
substance that is composed of two or more elements.
Ceramics are compounds between metallic and nonmetallic elements; they are most
frequently oxides, nitrides, and carbides. E.g. aluminum oxide (or alumina, Al2O3),
silicon dioxide (or silica, SiO2), silicon carbide (SiC), silicon nitride (Si3N4), and, the
traditional ceramics— composed of clay minerals (i.e., porcelain), as well as cement
and glass. Ceramic materials are typically insulative to the passage of heat and
electricity (i.e., have low electrical conductivities), and are more resistant to high
temperatures and harsh environments than metals and polymers. With regard to optical
characteristics, ceramics may be transparent, translucent, or opaque and some of the
oxide ceramics (e.g., Fe3O4) exhibit magnetic behavior.
Polymers include the familiar plastic and rubber materials. Many of them are organic
compounds that are chemically based on carbon, hydrogen, and other non-metallic
elements (i.e., O, N, and Si). E.g. polyethylene (PE), nylon, poly(vinyl chloride) (PVC),
polycarbonate (PC), polystyrene (PS), and silicone rubber. Furthermore, they have very
large molecular structures, often chainlike in nature, that often have a backbone of
carbon atoms. They have low electrical conductivities and are nonmagnetic.
A composite is composed of two (or more) individual materials, which come from the
categories previously discussed—metals, ceramics, and polymers. E.g. fiberglass,
carbon fiber–reinforced polymer(CFRP) The design goal of a composite is to achieve
a combination of properties that is not displayed by any single material, and also to
incorporate the best characteristics of each of the component materials. A large number
of composite types are represented by different combinations of metals, ceramics, and
polymers. Furthermore, some naturally occurring materials are composites—for
example, wood and bone.
Materials that are utilized in high-technology (or high-tech) applications are sometimes
termed advanced materials. By high technology we mean a device or product that
operates or functions using relatively intricate and sophisticated principles; examples
include electronic equipment, computers, fiber-optic systems, spacecraft, aircraft, and
military rocketry. These advanced materials are typically traditional materials whose
properties have been enhanced, and also newly developed, high-performance materials.
Furthermore, they may be of all material types (e.g., metals, ceramics, polymers), and
are normally expensive.
Semiconductors have electrical properties that are intermediate between the electrical
conductors (i.e., metals and metal alloys) and insulators (i.e., ceramics and polymers).
Furthermore, the electrical characteristics of these materials are extremely sensitive to
the presence of minute concentrations of impurity atoms, for which the concentrations
may be controlled over very small spatial regions. Semiconductors have made possible
the advent of integrated circuitry that has totally revolutionized the electronics and
computer industries (not to mention our lives) over the past three decades.
Biomaterials are employed in components implanted into the human body to replace
diseased or damaged body parts. These materials must not produce toxic substances
and must be compatible with body tissues (i.e., must not cause adverse biological
reactions). All of the preceding materials—metals, ceramics, polymers, composites,
and semiconductors—may be used as biomaterials.
Smart (or intelligent) materials are a group of new and state-of-the-art materials now
being developed that will have a significant influence on many of our technologies. The
adjective smart implies that these materials are able to sense changes in their
environment and then respond to these changes in predetermined manners—traits that
are also found in living organisms. In addition, this “smart” concept is being extended
to rather sophisticated systems that consist of both smart and traditional materials.
One new material class that has fascinating properties and tremendous technological
promise is the nanomaterials. Nanomaterials may be any one of the four basic types—
metals, ceramics, polymers, and composites. However, unlike these other materials,
they are not distinguished on the basis of their chemistry, but rather, size; the nano-
prefix denotes that the dimensions of these structural entities are on the order of a
nanometer (10–9 m)—as a rule, less than 100 nanometers (equivalent to approximately
500 atom diameters). E.g. Graphene, Carbon nanotube, quantum dot etc.
Crystal Structure:
In terms of atomic arrangement solids can be classified into mainly two categories: i)
Crystalline and ii) Amorphous.
Crystalline materials exhibit periodic arrangement of atoms. A definite repetitive
pattern is observed.
Amorphous materials have random arrangement of atoms.
Crystalline solids can be further classified into two categories: i) Monocrystalline and
ii) Polycrystalline
Monocrystalline materials exhibit single periodic arrangement of atoms throughout.
Polycrystalline materials exhibit a periodic arrangement of atoms for some region
another periodic arrangement of atoms for some different region and/or so on.
When viewed through naked eye any crystalline material appears to be featureless but
upon viewed through optical microscope it starts showing certain features.
These regions are called grains and the lines are called grain boundaries.
As they are observed when viewed through microscope they are known as
microstructures also.
A lattice can have several (infinitely many) translations, a collection of all these
translational symmetries is called the translational group of the lattice. Translational
group contains all lattice translations.
A lattice can have several non-translational symmetry, a collection of all these point
symmetry operations is called the point group of the lattice.
A collection of all symmetry operations (translational + point) is together called the
space group of the lattice.
Any 3D lattice can have only one of the 7 different kinds of rotational and reflection
symmetry or point groups which accounts for 7 crystal systems.
Similarly, any 3D lattice can have only one of the 14 different kinds of translational,
rotational and reflection i.e. complete symmetry or space groups which accounts for 14
Bravais lattices.
If it has only one-fold point symmetry
which means no special symmetry
then the crystal system (the least
symmetric crystal system) is called
triclinic.
If it has a single 2-fold point
symmetry (w.r.t. the axis joining the
face centres of the parallel faces
having sides a and c) then the crystal
system is called monoclinic.
If it has a single 3-fold point
symmetry (w.r.t. the axis along
lengthiest body diagonal) then the
system is called trigonal or
rhombohedral.
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If it has a single 6-fold point symmetry (w.r.t. the axis joining the face centers of the
hexagonal faces) then the system will be called a hexagonal crystal system.
If we have three 2-fold point symmetry (3 mutually orthogonal 2-fold axes formed by
joining the centres of opposite faces) then it is called orthorhombic.
If it has a single 4-fold point symmetry (axes formed by joining the centres of both
square size opposite faces) then we call it tetragonal.
Finally, the most symmetric one is the cubic crystal system. It is characterized by four
3-fold point symmetry (along all the body diagonals although it has other point
symmetries like 4-fold, 2-fold and mirror planes etc.)
Why cubic C was absent from the Bravais list?
So, if rotated by 120° along body diagonal, it is not coming to self-coincidence and
hence the three-fold symmetry is lost and this confirms that it is not a cubic lattice.
Further, if we observe, it actually have a
single 4-fold axes of symmetry which
indicates it to be a tetragonal lattice rather
than a cubic.
Similarly if we observe any other structure
that are absent from Bravais lattice list,
they will in fact turn out to be a different
lattice already defined in the list in terms of
symmetry. There, sometime the edge
length may not be exactly as per
requirement of a crystal system but still we
will put them in that system giving priority
to symmetry.
Crystal Directions and Planes:
In crystallography, we need to specify or name different directions and planes in a
crystal. Miller indexing of directions and planes are standard methods which are being
used for this purpose.
Steps of Miller indexing of directions :
1. The first step in Miller in indexing is to choose an origin on the direction as in the
crystallographic coordinate system, we are free to choose the origin. The origin
always has to be on the direction or vice versa, the direction should pass through
the origin.
2. The next step is to choose a crystallographic coordinate system with axis parallel to
the unit cell edges (even if they are not orthonormal in a non-cubic crystal) as this
is what is called the crystallographic coordinate system. Also, if already some
crystallographic axes were defined w.r.t. an origin, then for a new origin in that
same crystal system, the new axes must be parallel to the earlier axes also.
3. The next step is to find the coordinates of another convenient point on the direction
itself in terms of the lattice parameters ‘a’, ‘b’ and ‘c’ and hence take these
coefficients of ‘a’, ‘b’ and ‘c’ to represent this direction.
4. The next step is to reduce those coefficients to smallest integers and this can be
done either by dividing all by their highest common factor (if we have all integer
values) or multiplying by the lowest common multiplier of their denominator (if we
have any fractional value among them). For negative no, put a bar above.
5. The final step is to just put these three numbers in a square bracket [ ] as it is an
internationally agreed upon convention for Miller indices of any direction. Also
unless and until we have a 2 digit Miller indices for one of the components, we
should not use any comma to separate them.
Unlike vectors, Miller indices of a direction represents only the orientation of the line,
not its particular position in the crystal space. So, all parallel directions have the same
Miller indices.
To find Miller indices of directions,
OA and PQ:
Considering O to be origin and
defining crystal edges passing
through O as X,Y and Z axis, OA is
a/2 + b/2 + c
→ ½ ½ 1
→ [112]
Again now considering P to be
origin and defining crystal edges
passing through P and parallel to
previous axes as X,Y and Z axis, PQ
is – 1a – 1b + 1c
→ –1 –1 1
→ [ 1̅ 1̅ 1 ]
AG = [1 1 1] ; BI = [2 1̅ 1] ; CF = [1̅ 0 1] ̅̅̅̅ 11 20 ]
IJ = [20
Sometime we are not interested in just one direction because crystals can have
symmetry and symmetry relates many directions. So many directions become
equivalent. For example, if you take a cubic crystal, all the edges of the cube are
equivalent by the cubic symmetry. If we index the edge along x axis it will be [100] or
[1̅00], if we index along the y axis [010] or [01̅0] and indexed along z axis, [001] or
[001̅]. But if one is not interested in a specific direction, just want to talk about the cube
edges for all directions along the cube edges which are equivalent by symmetry then
<100> should be used as <uvw> means the specific direction [uvw] and all other
direction related to [uvw] by the symmetry of the crystal.
It is important that when we are using < > notation we have to know which crystal
system we are talking about because different crystals will have different symmetries
and the same symbol may mean different things. For example, <100> in cubic crystal
(a=b=c) mean any of [100], [1̅00], [010], [01̅0], [001] or [001̅] but in tetragonal
(a=b≠c) it means any of [100], [1̅00], [010] or [01̅0] only.
Steps of Miller indexing of planes :
1. The first step in Miller in indexing is to choose an origin not on the plane as in the
crystallographic coordinate system, we are free to choose the origin.
2. The next step is to choose a crystallographic coordinate system with axis parallel to
the unit cell edges (even if they are not orthonormal in a non-cubic crystal) as this
is what is called the crystallographic coordinate system. Also, if already some
crystallographic axes were defined w.r.t. an origin, then for a new origin in that
same crystal system, the new axes must be parallel to the earlier axes also.
3. The next step is to find the intercepts along axis in terms of the lattice parameters
‘a’, ‘b’ and ‘c’ and hence take these coefficients of ‘a’, ‘b’ and ‘c’ to represent this
plane.
4. Take reciprocal of intercepts.
5. The next step is to reduce those coefficients to smallest integers if and only if the
plane is passing through any of the corner points and this can be done either by
dividing all by their highest common factor (if we have all integer values) or
multiplying by the lowest common multiplier of their denominator (if we have any
fractional value among them). If the plane is not passing through any of the corner
points then no need to do this reduction. For negative no, put a bar above.
6. The final step is to just put these three numbers in a round bracket i.e. parentheses
( ) as it is an internationally agreed upon convention for Miller indices of any plane.
Also unless and until we have a 2 digit Miller indices for one of the components,
we should not use any comma to separate them.
To find Miller indices of the triangular plane,
considering O to be origin and defining crystal
edges passing through O as X,Y and Z axis,
intercepts of the given plane are: 1a, 1b, 1c
→111
→111
→111
→(1 1 1)
To find Miller indices of ABCD plane, considering
O to be origin and defining crystal edges passing
through O as X,Y and Z axis, intercepts of the given
plane are: 1a, ∞b, ∞c
→1∞∞
→100
→100
→(1 0 0)
To find Miller indices of EBCO plane, shifting
origin to O* and defining crystal edges passing
through O as X,Y and Z axis, intercepts of the given
plane are: 1a, -1b, ∞c
→ 1 -1 ∞
→ 1 -1 0
→ 1 -1 0
→ (1 1̅ 0)
Intercepts: 1a, 3b, 2c
→132
→ 1 1/3 1/2
→623
→ (6 2 3)
z
Note: Miller indices are the reciprocal of the intercepts in terms of the corresponding lattice
parameters.
𝑑ℎ𝑘𝑙
Inter planar spacing of two parallel consecutive (h k l) and (nh nk nl) plane is = 𝑛
An X-ray detector placed at an angle 2θ with respect to the transmitted beam will register
a peak in the detected X-ray intensity.
The instrument that allows this type of X-ray diffraction study is called a diffractometer.
The variation of the detected intensity with the diffraction angle 2θ represents the
diffraction pattern of the crystal.
We use 2θ i.e. angle of detector with respect to the transmitted beam for plotting the
diffraction pattern as θ is not directly available during expriment as we don’t know the
position or orientation of the crystal planes inside the crystal.
The diffraction pattern intensity analysis gives clearer understanding regarding the crystal
i.e. relative atomic density of the corresponding atomic planes although position of the
peaks already gives idea regarding the crystal i.e. regarding available atomic planes.
#
= 3.75 cm
Crystal imperfections or defects:
Real crystals show deviations from ideality and are termed as defects or imperfections.
They are very important topic in material science because these defects or imperfections
control the properties of material.
Defects can be classified based on dimensionality into three categories:
a) Zero dimensional or point defects e.g. vacancy, interstitial and substitutional
defects,
b) One dimensional or line defects e.g. edge and screw dislocation defects,
c) Two dimensional or surface defects e.g. free surface, grain boundary, twin
boundary, stacking fault defects.
Vacancy defects:
In an ideal single-crystal lattice, the atoms are arranged in
a perfect periodic arrangement. However, in a real crystal,
an atom may be missing from a particular lattice site. This
defect is referred to as a vacancy.
It is found that at any temperature other than absolute
zero, under thermodynamic equilibrium i.e. at constant
temperature and pressure, there must be certain fraction
of vacant sites in a crystal as it minimizes the Gibbs free
energy of the system.
If the number of atoms per unit volume in the crystal is N and Ev is the average energy
required to create a vacancy, then the vacancy concentration nv is given by
𝐸
𝑛𝑣 = 𝑁 exp( 𝑘𝑇𝑣 )