Chapter 2. Atomic Structure, Interatomic Bonding and Structure of PDF

Material Sccience Prof. Satish V.
Kailas
Material Science
Prof. Satish V. Kailas

Associate Professor
Dept. of Mechanical Engineering,
Indian Institute of Science,
Bangalore – 560012
India
Chapter 2. Atomic Structure, Interatomic Bonding and Structure of

Crystalline Solids
Learning objectives:
- To get an idea about composition of an atom, and to know about different bonds in solids,
and be able to distinguish between them.
- Shall be able to find atomic density of a material.
- To understand the concepts of unit cell, crystal structure.
- Be able to construct different directions and planes in crystals with proper notation.
- Understand the concept of anisotropy.
- Elastic nature of composites.
- Structure and properties of Polymers and Ceramics.
Indian Institute of Science Bangalore

Material Sccience Prof. Satish V. Kailas
Material Science

Associate Professor
India
Chapter 2. Atomic Structure, Interatomic Bonding and Structure of

Crystalline Solids
Highlights, Motivation and Critical Concepts:
Atoms are the very basic unit of the universe, every thing in this universe is made up of atoms.
Basically atoms are the building blocks. Yes, What ever you see around you is made up of atoms!
Atoms are very small particles. A tip of sharpened pencils has thousands of atoms. But, atoms are not
the smallest particles! There are even smaller particles.
You know the universe is made up of atoms. Do you know the atoms are made up of what? The
atoms are made up of very, very, very small and three different types of particles, namely the
Electrons, Protons and Neutrons. An atom is composed of electrons, protons, and neutrons, which are
in specific number and arranged in specific order in each of the elements. Solid materials consists
number of atoms of either same element or different elements. They are mainly three kinds – metals,
polymers, and ceramics. Different kinds of bonds exist to keep atoms together, and these bonds
dictates the way materials behave. Many of the engineering properties of materials depend on the
arrangement of atoms in solids. Special notations are needed to describe the atomic arrangement in
solids. No wonder that not any two materials behave in the same fashion as there exists millions of
combinations of chemical composition, bonds, and atomic arrangement.

Material Science

Associate Professor
India
Chapter 2. Atomic Structure, Interatomic Bonding and Structure

of Crystalline Solids
2.1 Atomic Structure and Atomic Bonding in Solids
2.1.1 Atomic Structure
Atoms are composed of electrons, protons, and neutrons. Electrons and protons are
negative and positive charged particles respectively. The magnitude of each charged
particle in an atom is 1.6 × 10-19 Coulombs.
The mass of the electron is negligible with respect to those of the proton and the neutron,
which form the nucleus of the atom. The unit of mass is an atomic mass unit (amu) =
1.66 × 10-27 kg, and equals 1/12 the mass of a carbon atom. The Carbon nucleus has Z=6,
and A=6, where Z is the number of protons, and A the number of neutrons. Neutrons and
protons have very similar masses, roughly equal to 1 amu each. A neutral atom has the
same number of electrons and protons, Z.
A mol is the amount of matter that has a mass in grams equal to the atomic mass in amu
of the atoms. Thus, a mole of carbon has a mass of 12 grams. The number of atoms in a
mole is called the Avogadro number, Nav = 6.023 × 1023. Note that Nav = 1 gram/1 amu.
Calculating n, the number of atoms per cm3 of a material of density δ (g/cm3):
δ
n = N av
M
where M is the atomic mass in amu (grams per mol). Thus, for graphite (carbon) with a
density δ = 1.8 g/cm3, M =12, we get 6 × 1023 atoms/mol × 1.8 g/cm3 / 12 g/mol) = 9 ×
1022 C atoms/cm3.

For a molecular solid like ice, one uses the molecular mass, M(H2O) = 18. With a density
of 1 g/cm3, one obtains n = 3.3 × 1022 H2O molecules/cm3. Note that since the water
molecule contains 3 atoms, this is equivalent to 9.9 × 1022 atoms/cm3.
Most solids have atomic densities around 6 × 1022 atoms/cm3. The cube root of that
number gives the number of atoms per centimeter, about 39 million. The mean distance
between atoms is the inverse of that, or 0.25 nm. This is an important number that gives
the scale of atomic structures in solids.
2.1.2 Atomic bonding in solids
In order to understand the why materials behave like they do and why they differ in
properties, it is necessary that one should look at atomic level. The study primarily
concentrates on two issues: what made the atoms to cluster together, and how atoms are
arranged. As mentioned in earlier chapter, atoms are bound to each other by number of
bonds. These inter-atomic bonds are primarily of two kinds: Primary bonds and
Secondary bonds. Ionic, Covalent and Metallic bonds are relatively very strong, and
grouped as primary bonds, whereas van der Waals and hydrogen bonds are relatively
weak, and termed as secondary bonds. Metals and Ceramics are entirely held together by
primary bonds - the ionic and covalent bonds in ceramics, and the metallic and covalent
bonds in metals. Although much weaker than primary bonds, secondary bonds are still
very important. They provide the links between polymer molecules in polyethylene (and
other polymers) which make them solids. Without them, water would boil at -80˚C, and
life as we know it on earth would not exist.
Ionic Bonding: This bond exists between two atoms when one of the atoms is negative
(has an extra electron) and another is positive (has lost an electron). Then there is a
strong, direct Coulomb attraction. Basically ionic bonds are non-directional in nature. An
example is NaCl. In the molecule, there are more electrons around Cl, forming Cl- and
fewer electrons around Na, forming Na+. Ionic bonds are the strongest bonds. In real
solids, ionic bonding is usually exists along with covalent bonding.
Na Cl
Fig.1 Schematic representation of ioning bonding. Here, Na is giving an electron to Cl to

have stable structure

Covalent Bonding: In covalent bonding, electrons are shared between the atoms, to
saturate the valency. The simplest example is the H2 molecule, where the electrons spend
more time in between the nuclei of two atoms than outside, thus producing bonding.
Covalent bonds are stereo-specific 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. The hardness of diamond is a result of the fact
that each carbon atom is covalently bonded with four neighboring atoms, and each
neighbor is bonded with an equal number of atoms to form a rigid three-dimensional
structure.
H H
Figure 2. Schematic representation of covalent bond in Hydrogen molecule (sharing of

electrons)
Metallic Bonding: Metals are characterized by high thermal and electrical

conductivities. Thus, neither covalent nor ionic bondings are realized because both types
of bonding localize the valence electrons and preclude conduction. However, strong
bonding does occur in metals. The valence electrons of metals also are delocalized. Thus
metallic bonding can be viewed as metal containing a periodic structure of positive ions
surrounded by a sea of delocalized electrons. The attraction between the two provides the
bond, which is non-directional.
Electron cloud from
the valence electrons
M M M M
M M M M Core
M M M M
M M M M

Figure 3. Metallic bonding
Fluctuating Induced Dipole Bonds: Since the electrons may be on one side of the atom
or the other, a dipole is formed: the + nucleus at the center, and the electron outside.
Since the electron moves, the dipole fluctuates. This fluctuation in atom A produces a
fluctuating electric field that is felt by the electrons of an adjacent atom, B. Atom B then
polarizes so that its outer electrons are on the side of the atom closest to the + side (or
opposite to the – side) of the dipole in A.
Polar Molecule-Induced Dipole Bonds: Another type of secondary bond exists with
asymmetric molecules, also called polar molecules because of positively and negatively
charged regions. A permanent dipole moment arises from net positive and negative
charges that are respectively associated with the hydrogen and chlorine ends of the HCl
molecule, leading to bonding. The magnitude of this bond will be greater than for
fluctuating induced dipoles.
Figure 4. Dipole bond in water
These two kinds of bonds are also called van der Waals bonds. Third type of secondary
bond is the hydrogen bond. It is categorized separately because it produces the strongest
forces of attraction in this category.
Permanent Dipole Bonds / Hydrogen bonding: It occurs between molecules as

covalently bonded hydrogen atoms – for example C-H, O-H, F-H – share single electron
with other atom essentially resulting in positively charged proton that is not shielded any
electrons. This highly positively charged end of the molecule is capable of strong
attractive force with the negative end of an adjacent molecule. The properties of water are
influenced significantly by the hydrogen bonds/bridges. The bridges are of sufficient
strength, and as a consequence water has the highest melting point of any molecule of its
size. Likewise, its heat of vaporization is very high.

2.2 Crystal Structures, Crystalline and Non-Crystalline materials
2.2.1 Crystal structures
All metals, a major fraction of ceramics, and certain polymers acquire crystalline form
when solidify, i.e. in solid state atoms self-organize to form crystals. Crystals possess a
long-range order of atomic arrangement through repeated periodicity at regular intervals
in three dimensions of space. When the solid is not crystalline, it is called amorphous.
Examples of crystalline solids are metals, diamond and other precious stones, ice,
graphite. Examples of amorphous solids are glass, amorphous carbon (a-C), amorphous
Si, most plastics.
There is very large number of different crystal structures all having long-range atomic
order; these vary from relatively simple structures for metals to exceedingly complex
structures for ceramics and some polymers. To discuss crystalline structures it is useful to
consider atoms as being hard spheres, with well-defined radii. In this scheme, the shortest
distance between two like atoms is one diameter. In this context, use of terms lattice and
unit cell will be handy. Lattice is used to represent a three-dimensional periodic array of
points coinciding with atom positions. Unit cell is smallest repeatable entity that can be
used to completely represent a crystal structure. Thus it can be considered that a unit cell
is the building block of the crystal structure and defines the crystal structure by virtue of
its geometry and the atom positions within.
Important properties of the unit cells are
• The type of atoms and their radii R.

• Cell dimensions (Lattice spacing a, b and c) in terms of R and
• Angle between the axis α, β, γ
• a*, b*, c* - lattice distances in reciprocal lattice , α*, β*, γ* - angle in reciprocal
lattice
• n, number of atoms per unit cell. For an atom that is shared with m adjacent unit
cells, we only count a fraction of the atom, 1/m.
• CN, the coordination number, which is the number of closest neighbors to which
an atom is bonded.
• APF, the atomic packing factor, which is the fraction of the volume of the cell
actually occupied by the hard spheres. APF = Sum of atomic volumes/Volume of
cell.
Some very common crystal structures and relevant properties are listed in table 2.1.
Table 2.1: Common crystal structures and their properties.
Unit Cell n CN a/R APF
Simple Cubic 1 6 4/√4 0.52

Body-Centered Cubic 2 8 4/√ 3 0.68
Face-Centered Cubic 4 12 4/√ 2 0.74
Hexagonal Close Packed 6 12 0.74
Figure 2.1: Common metallic crystal structures.
2.2.2 Crystalline and Non-crystalline materials
Single Crystals: Crystals can be single crystals where the whole solid is one crystal.
Then it has a regular geometric structure with flat faces.
Polycrystalline Materials: A solid can be composed of many crystalline grains, not

aligned with each other. It is called polycrystalline. The grains can be more or less
aligned with respect to each other. Where they meet is called a grain boundary.
Non-Crystalline Solids: In amorphous solids, there is no long-range order. But

amorphous does not mean random, since the distance between atoms cannot be smaller
than the size of the hard spheres. Also, in many cases there is some form of short-range
order. For instance, the tetragonal order of crystalline SiO2 (quartz) is still apparent in
amorphous SiO2 (silica glass).
2.3 Miller Indices, Anisotropy, and Elastic behavior of composites
2.3.1 Miller indices:
It is understood that properties of materials depend on their crystal structure, and many of
these properties are directional in nature. For example: elastic modulus of BCC iron is
greater parallel to the body diagonal than it is to the cube edge. Thus it is necessary to
characterize the crystal to identify specific directions and planes. Specific methods are
employed to define crystal directions and crystal planes.
Methodology to define crystallographic directions in cubic crystal:

- a vector of convenient length is placed parallel to the required direction.

- the length of the vector projection on each of three axes are measured in unit cell
dimensions.
- these three numbers are made to smallest integer values, known as indices, by
multiplying or dividing by a common factor.
- the three indices are enclosed in square brackets, [uvw]. A family of directions is
represented by <uvw>.
Methodology to define crystallographic planes in cubic crystal:
- determine the intercepts of the plane along the crystallographic axes, in terms of
unit cell dimensions. If plane is passing through origin, there is a need to construct
a plane parallel to original plane.
- take the reciprocals of these intercept numbers.
- clear fractions.
- reduce to set of smallest integers.
- The three indices are enclosed in parenthesis, (hkl). A family of planes is
represented by {hkl}.
For example, if the x-, y-, and z- intercepts of a plane are 2, 1, and 3. The Miller indices
are calculated as:
- take reciprocals: 1/2, 1/1, 1/3.
- clear fractions (multiply by 6): 3, 6, 2.
- reduce to lowest terms (already there). => Miller indices of the plane are (362).
Figure 2.2 depicts Miller indices for number of directions and planes in a cubic crystal.
Figure 2.2: Miller indices in a cubic crystal.
Some useful conventions of Miller notation:
- If a plane is parallel to an axis, its intercept is at infinity and its Miller index will
be zero.

- If a plane has negative intercept, the negative number is denoted by a bar above
the number. Never alter negative numbers. For example, do not divide -1, -1, -1
by -1 to get 1,1,1. This implies symmetry that the crystal may not have!
- The crystal directions of a family are not necessarily parallel to each other.
Similarly, not all planes of a family are parallel to each other.
- By changing signs of all indices of a direction, we obtain opposite direction.
Similarly, by changing all signs of a plane, a plane at same distance in other side
of the origin can be obtained.
- Multiplying or dividing a Miller index by constant has no effect on the orientation
of the plane.
- The smaller the Miller index, more nearly parallel the plane to that axis, and vice
versa.
- When the integers used in the Miller indices contain more than one digit, the
indices must be separated by commas. E.g.: (3,10,13)
- By changing the signs of all the indices of (a) a direction, we obtain opposite
direction, and (b) a plane, we obtain a plane located at the same distance on the
other side of the origin.
More conventions applicable to cubic crystals only:
- [uvw] is normal to (hkl) if u = h, v = k, and w = l. E.g.: (111) ┴ [111].

- Inter-planar distance between family of planes {hkl} is given by:
a
d {hkl} =
h + k2 + l2
2
- [uvw] is parallel to (hkl) if hu + kv + lw = 0.

- Two planes (h1k1l1) and (h2k2l2) are normal if h1h2 + k1k2 + l1l2=0.
- Two directions (u1v1w1) and (u2v2w2) are normal if u1u2 + v1v2 + w1w2=0
- Angle between two planes is given by:
h1 h2 + k1 k 2 + l1l 2
cos θ =
h12 + k12 + l12 h22 + k 22 + l 22
The same equation applies for two directions.
Why Miller indices are calculated in that way?

- Using reciprocals spares us the complication of infinite intercepts.
- Formulas involving Miller indices are very similar to related formulas from
analytical geometry.
- Specifying dimensions in unit cell terms means that the same label can be applied
to any plane with a similar stacking pattern, regardless of the crystal class of the
crystal. Plane (111) always steps the same way regardless of crystal system.
2.3.2 Miller-Bravis indices

Though Miller indices can describe all possible planes through any crystal, Miller-Bravis
indices are used in hexagonal crystal systems. This is because they reveal hexagonal
symmetry more clearly. Although partially redundant, they are used exclusively for
hexagonal systems.
Direction indices are obtained as above where first three indices are representative of
projections of the direction over three co-planar axes in the plane called basal plane while
the last index denotes the projection over the axis perpendicular to the basal plane.
Miller-Bravis indices for a plane are denoted as [uvtw], where t = -(u+v)
In the same procedure, planes in a hexagonal crystal are denoted by (hkil), where i = -
(h+k).
2.3.3 Anisotropy
It’s been agreed that many of the materials properties depend on the crystal structure.
However, crystals are not symmetric in all directions, or not the crystal planes same with
respect to atomic density/packing. Different directions in the crystal have different
packing. For instance, atoms along the edge of FCC crystals are more separated than
along its face diagonal. This causes properties to be different in different directions. This
directionality of properties is termed as Anisotropy.
Substances in which measured properties are independent of direction in which they are
measured are called isotropic. Though, in polycrystalline materials, the crystallographic
orientations of individual grains are random, specimen may behave isotropically.
2.3.4 Elastic Behavior of Composites
The idea is that by combining two or more distinct materials one can engineer a new
material with the desired combination of properties (e.g., light, strong, corrosion
resistant). The idea that a better combination of properties can be achieved is called the
principle of combined action.
For example, Pearlitic steel that combines hard and brittle Cementite with soft and ductile
ferrite to get a superior material.
A composite is defined as a artificially made muti-phase material, where constituent

phases are chemically dissimilar and separated by a distinct interface. Thus, composites
shall have at least two or more constituent phases. Many of the composites are made of
two phases – one is termed as matrix, which is continuous and surrounds the other phase,
called dispersed phase. Dispersed phase can exist in many forms like particulates, short-
/long- fibers.
Properties of composites depend on

- Properties of the constituent phases.

- Geometry of dispersed phase (particle size, size distribution, orientation).
- Amount of each constituent phase.
Classification of composites based on geometry of dispersed phase:

- Particle-reinforced (large-particle and dispersion-strengthened)
- Fiber-reinforced (continuous (aligned) and short fibers (aligned or random)
- Structural (laminates and sandwich panels)
Classification of composites based on matrix phase:

- Metal Matrix Composites.
- Polymer Matrix Composites.
- Ceramic Matrix Composites.
Composite properties can be calculated using rule of mixtures. For example, elastic
modulus of a particle reinforced composite bound by the limits given by
E c (u ) = E mVm + E pV p
Em E p
E c (l ) =
E mV p + E pVm
where E and V denote the elastic modulus and volume fraction respectively; c, m, and p
represent composite, matrix, and particulate phases.
However, in case of continuous fiber reinforced composites upper bound is applicable to

condition of longitudinal loading, while the lower bound is applicable to transverse
loading condition. The above equations can be simplified using the following relations:
Vm + V p = 1
When fiber orientation is random, or short and discontinuous fibers are used, rule of
mixtures will be modified as follows to take care of the randomness of fibers:
E cd = E mVm + KE f V f
where K – is fiber efficiency parameter that depends on Vf and Ef/Em ratio. K’s values are
less than unity, usually attains a value in the range of 0.1 to 0.6.
Many applications, like in aircraft parts, there is a need for high strength per unit weight
(specific strength). This can be achieved by composites consisting of a low-density (and
soft) matrix reinforced with stiff fibers.
2.4 Structure and properties of polymers

Polymers are common in nature, in the form of wood, rubber, cotton, leather, wood, silk,
proteins, enzymes, starches, cellulose. Artificial polymers are made mostly from oil.
Their use has grown exponentially, especially after WW2 (World War-2). The key factor
is the very low production cost and useful properties (e.g., combination of transparency
and flexibility, long elongation, etc.).
Most polymers are organic, and formed from hydrocarbon molecules. These molecules
can have single, double, or triple carbon bonds. A saturated hydrocarbon is one where
all bonds are single, i.e. the number of atoms is maximum (or saturated). Among this type
are the paraffin compounds, CnH2n+2. In contrast, non-saturated hydrocarbons contain
some double and triple bonds.
Isomers are molecules that contain the same molecules but in a different arrangement.
An example is butane and iso-butane. Some physical properties of hydrocarbons depend
on the isomeric state.
2.4.1 Polymer molecules
Polymer molecules are huge, macromolecules that have internal covalent bonds. For most
polymers, these molecules form very long chains. The backbone is a string of carbon
atoms, often single bonded. Polymers are composed of basic structures called mer
units. A molecule with just one mer is a monomer. Within each molecule / mer atoms are
bonding together by strong covalent bonds. When many mers are together, they form
polymer. Bi-functional monomers may bond with two other units in forming 2-D chain-
like structures; while Tri-functional monomers can form three active bonds, and thus 3-D
molecular network. Examples of polymers are polyvinyl chloride (PVC), poly-tetra-
fluoro-ethylene (PTFE or Teflon), polypropylene, nylon and polystyrene. When all the
mers are the same, the molecule is called a homopolymer. When there is more than one
type of mer present, the molecule is a copolymer.
The mass of a polymer is not fixed, but is distributed around a mean value, since not all
polymer chains will grow same extent. The average molecular weight can be obtained by
averaging the masses with the fraction of times they appear (number-average) or with the
weight fraction of the molecules (weight-average). Another representation of average
chain size is degree of polymerization (n) – average number of mer units in a chain. It is
obtained by dividing the average mass of the polymer by the mass of a mer unit.
Numbers of polymer characteristics are affected by the magnitude of the molecular
weight. Short chain polymers usually exist in form of gases or liquids at room
temperature; where as medium range polymers are waxy solids and soft resins. Solid
polymers are commonly having weights ranging between 10K and several million g/mol.
2.4.2 Polymer structures
Polymers consist of large number of molecular chains which are usually not linear;
bending and rotations can occur around single C-C bonds (double and triple bonds are
very rigid). Random kinks and coils in chains along with bending of chains lead to

intertwining and entanglement of neighboring chains, situation like in the spaghetti

structure. These characteristic entanglements are responsible for a number of properties
specific to polymers, e.g.: large elastic extension. However, physical properties of
polymers depend not only on molecular weight and shape, but also on differences in
structure of the chains. It should be remembered that polymers are not usually of only one
distinctive structural type, though they are classified into different groups. Typical
polymer chain structures are: (a) linear, where mer units are joined together end to end in
single chains. E.g.: PVC, nylon. (b) branched, where side-branch chains are connected to
main ones. Branching of polymers lowers polymer density because of lower packing
efficiency. (c) cross-linked, where chains are joined one to another at various positions by
covalent bonds. This cross-linking is usually achieved at elevated temperatures by
additive atoms. E.g.: vulcanization of rubber. (d) network, trifunctional mer units with 3-
D networks comes under this category. E.g.: epoxies, phenol-formaldehyde.
2.4.3 Polymer crystallinity
Crystallinity in polymers is more complex than in metals. Polymer molecules are often
partially crystalline (semicrystalline), with crystalline regions dispersed within
amorphous material. The degree of crystallinity may range from completely amorphous
to almost entirely crystalline; on the other hand metals are almost always crystalline
whereas ceramics are either completely crystalline or noncrystalline. The degree of
crystallinity of a polymer depends on cooling path, and also on chain configuration. For
copolymers, the more irregular and random the mer arrangement, the greater is
probability for noncrystalline nature. Crystalline polymers are denser than amorphous
polymers, so the degree of crystallinity can be obtained from the measurement of density.
Different models have been proposed to describe the arrangement of molecules in

semicrytalline polymers. In the fringed-micelle model, the crystallites (micelles) are
embedded in an amorphous matrix. Polymer single crystals grown are shaped in regular
platelets (lamellae). Spherulites are chain-folded crystallites in an amorphous matrix that
grow radially in spherical shape “grains”. These are considered to be the polymer
analogue of grains in polycrystalline metals and ceramics. Many semicrystalline
polymers form spherulites; each spherulite consists of a collection of ribbonlike chain-
folded lamellar crystallites that radiate outward from its center. E.g.: polyethelene, PVC.
A polymer’s response to mechanical forces under elevated temperatures is related to its

molecular structure. Based on this response, polymers are classified as: thermoplasts
(soften when heated and harden when cooled), and thermosets (become permanently hard
when heat is applied and do not soften upon subsequent heating). Thermosets are
generally harder and stronger than thermoplasts, and have better dimensional stability.
Most of the cross-linked and network polymers are thermosets; whereas linear and some
branched polymers are thermoplasts.
2.4.4 Properties of polymers

Fluids and amorphous solids undergo viscous flow when external forces are applied. It is
well known that polymers exhibit very high viscosity in order of 1012 Pa.s at room
temperature. Polymers are non-Newtonian in nature, and formed into plastic products at a
temperature above their glass-transition temperature. It is evident that temperature has
very strong influence on mechanical behavior of polymers. Elastic strain occurs
simultaneously with viscous flow, resulting in visco-elastic deformation of polymers
under externally applied loads. Below the glass transition temperature elastic deformation
dominates and the material behaves rigid. In the range of glass temperature, the materials
is leathery; in the rubber plateau, polymers deform readily but quickly regain their
previous shape if the stress in removed. At still higher temperatures, under sustained
loads, the polymer deforms extensively by viscous flow. Figure below depicts
temperature effect on deformation behavior of polymers.
Figure 2.3: Dependence of polymer viscosity on temperature and/or loading rate.
2.5 Structure and properties of ceramics
Ceramics are inorganic and non-metallic materials that are commonly electrical and
thermal insulators, brittle and composed of more than one element (e.g., two in Al2O3).
As ceramics are composed of two or more elements, their crystal structures are generally
more complex than those of metals. Ceramic bonds are mixed, ionic and covalent, with a
proportion that depends on the particular ceramics. The ionic character is given by the
difference of electronegativity between the cations (+) and anions (-). Covalent bonds
involve sharing of valence electrons. Very ionic crystals usually involve cations which

are alkalis or alkaline-earths (first two columns of the periodic table) and oxygen or
halogens as anions.
The building criteria for the ceramic crystal structure are as follows:
- maintain neutrality (charge balance dictates chemical formula)
- achieve closest packing
The crystal stability condition i.e. condition of minimum energy implies maximum
attraction and minimum repulsion. This leads to contact and configurations such that
anions have the highest number of cation neighbors (coordination number) and vice
versa. The coordination number is dependent on cation-anion radius ratio, which can be
determined from geometric relations. Table 2.2 presents relevant coordination numbers
and radius ratios.
Table 2.2. Co-ordination number dependency on cation-anion radius ratio.

Cation-anion 0.155 – 0.225 – 0.414 – 0.732 –
< 0.155 > 1.000
radius ratio (rc/ra) 0.225 0.414 0.732 1.000
Coordination
2 3 4 6 8 12
number
Figure-2.4 presents schematic arrangement of cations and anions with respective

coordinate positions for different radius ratios.
Figure 2.4: Ion arrangements for different coordination numbers.
2.5.1 Ceramic crystal structures
AX-type ceramic crystal structures: Most common ceramics are made of equal number of
cations and anions, and are referred to as AX compounds (A-cation, and X-anion). These
ceramics assume many different structures, named after a common material that
possesses the particular structure.

Rock salt structure: here the coordination number is 6, i.e. rc/ra = 0.414-0.732. This
structure can be viewed as an FCC of anions with cations occupying center of each edge
and the center of the cell. Thus it can be said that lattice is made of two interpenetrating
FCC lattices, one composed of cations, and the other of anions. E.g.: NaCl, MgO, FeO.
Cesium Chloride structure: here the coordination number is 8. Crystal structure consists
of anions at corners of a cube while a cation occupies the center, and vice versa. E.g.:
CsCl.
Zinc Blende structure: here the coordination number is 4. Unit cell is composed of one
kind of ions occupying corners and face centers of a cube, while the other kind of ions
occupies the interior tetrahedral positions. E.g.: ZnS, SiC.
AmXp- type structures: when the charges of cation and anions are not the same, to
maintain the neutrality, ceramic structures with chemical formula would exist. For
example – CaF2 with rc/ra = 0.8, and thus coordination number of 8. It can be expected
that crystal structure could be the same as that of CsCl. However cations are half many as
anions, thus only half the center positions are occupied. One unit cell shall be made of
eight cubes. E.g.: UO2, ThO2, PuO2.
AmBnXp-type structures: it is possible that ceramics do have more than one kind of
cations. E.g.: BaTiO3. unit cell is made of cube where Ba2+ ions occupies all eight
corners, T4+ occupies cube center, while O2- are at center of each face. This structure is
called perovskite crystal structure.
It is worth to understand and know more about some common most common ceramic in
nature. For example: silicates and carbon.
2.5.2 Silicates
Oxygen and Silicon are the most abundant elements in Earth’s crust. Their combination
(silicates) occurs in rocks, soils, clays and sand. The bond is weekly ionic, with Si4+ as
the cation and O2- as the anion. However the bonds in silicates are strongly of covalent
character with strong directional Si-O bonds. Basic unit of silicates structures are thus is
SiO44- tetrahedron that consists of four oxygen atoms at corners of tetrahedron, and
silicon atom at the center of it. Various silicate structures consists SiO44- unit bonded in
1-, 2-, and 3- dimensions.
In silica (SiO2) every oxygen atom is shared by adjacent tetrahedra. Silica can either be
crystalline (e.g., quartz) or amorphous, as in glass. Crystalline forms of silica are known
to be complicated and comparatively open, thus of low densities compared with
amorphous glasses. Soda glasses melt at lower temperature than amorphous SiO2 because
the addition of Na2O (soda) that act as network modifier breaks the tetrahedral network.
Addition of intermediates such as Al2O3, TiO2 substitute of silicon atoms and become
part of stabilized network. Addition of network modifiers and intermediates lowers
melting point, and thus it is easy to form glass, for instance, bottles.

In complicated silicate structure, corner oxygen atom of basic unit is shared by other
tetrahedra, resulting in formulas such as SiO44-, Si2O76-, Si3O96-, etc. The repeating unit of
2-D sheet or layered structure is represented as Si2O52-. Such layered structures are
characteristics of clays and other minerals.
2.5.3 Carbon
Carbon is not really a ceramic, but one of its allotropic form, diamond may be considered
as a ceramic. Diamond has very interesting and even unusual properties such as:
- possesses diamond-cubic structure (like Si, Ge)
- consists covalent C-C bonds
- having highest hardness of any material known
- very high thermal conductivity (unlike ceramics)
- transparent in the visible and infrared, with high index of refraction
- semiconductor (can be doped to make electronic devices)
- meta-stable (transforms to carbon when heated)
Synthetic diamonds are made by application of high temperatures and pressures or by

chemical vapor deposition. Future applications of this latter, cheaper production method
include hard coatings for metal tools, ultra-low friction coatings for space applications,
and microelectronics.
Graphite, another allotropic form of carbon, has a layered structure with very strong
hexagonal bonding within the planar layers (using 3 of the 3 bonding electrons) and
weak, van der Waals bonding between layers using the fourth electron. This leads to easy
inter-planar cleavage and applications as a lubricant and for writing (pencils). Graphite is
a good electrical conductor and chemically stable even at high temperatures. Applications
include furnaces, rocket nozzles, electrodes in batteries, etc.
Recently (1985) discovered allotropic form of carbon is the C60 molecule, also known as
fullerene or bucky-ball (after the architect Buckminster Fuller who designed the geodesic
structure that C60 resembles.). Structure of this form resembles a hallow spherical cluster
of 60 atoms, and is found to consist of 20 hexagons and 12 pentagons where no two
pentagons share a common edge. Fullerenes and related structures like nanotubes are
exceptionally stiff, strong, and ductile. Future applications of fullerenes are as a structural
material and possibly in microelectronics, due to the unusual properties that result when
fullerenes are doped with other atoms.
2.5.4 Imperfections in ceramics
Imperfections in ceramics include point defects and impurities. Their formation is

strongly affected by the condition of charge neutrality (creation of unbalanced charges
requires the expenditure of a large amount of energy). Both vacancies and interstitials are
possible in ceramics as in metals; however as ceramics have more then one element these
defects can be associated with each of these elements. Neutral charge defects include the
Frenkel and Schottky defects. A Frenkel-defect is a vacancy- interstitial pair of cations

(placing large anions in an interstitial position requires a lot of energy in lattice

distortion). A Schottky-defect is a pair of nearby cation and anion vacancies.
Non-stoichiometry refers to a change in composition so that the elements in the ceramic

are not in the proportion appropriate for the compound (condition known as
stoichiometry). To minimize energy, the effect of non-stoichiometry is a redistribution of
the atomic charges. Introduction of impurity atoms in the lattice is likely in conditions
where the charge is maintained. This is the case of electronegative impurities that
substitute lattice anions or electropositive substitutional impurities. This is more likely for
similar ionic radii since this minimizes the energy required for lattice distortion. Defects
will appear if the charge of the impurities is not balanced.
2.5.5 Mechanical response of ceramics
Brittle Fracture of Ceramics: The brittle fracture of ceramics limits their engineering
applications. It occurs due to the unavoidable presence of microscopic flaws (micro-
cracks, internal pores, and atmospheric contaminants) that result during cooling from the
melt. The flaws need to crack initiation, and crack propagation (perpendicular to the
applied stress) is usually trans-granular, along cleavage planes. The flaws cannot be
closely controlled in manufacturing; this leads to a large scatter in the fracture strength of
ceramic materials.
Under compressive stresses, however, flaws do not associate with amplification of stress.
Hence, the compressive strength of ceramics is typically ten times to their tensile
strength. This makes ceramics good structural materials under compression (e.g., bricks
in houses, stone blocks in the pyramids), but not in conditions of tensile stress, such as
under flexure.
Plastic deformation in crystalline ceramics is by slip, which is difficult due to the

structure and the strong local (electrostatic) potentials. There is very little plastic
deformation before fracture. Non-crystalline ceramics, like common glass, deform by
viscous flow (like very high-density liquids) as deformation can not occur by slip because
of absence of regular atomic structure, which occurs in metals. Characteristic property of
viscous flow, viscosity, is a measure of non-crystalline material’s resistance to
deformation. It was found to decrease with increasing temperature. At room temperature,
the viscosity of many non-crystalline ceramics is extremely high.
References
1. William D. Callister, Jr, Materials Science and Engineering – An introduction,

sixth edition, John Wiley & Sons, Inc. 2004.
2. B. D. Cullity and S. R. Stock, Elements of X-Ray Diffraction, Third Edition,
Prentice Hall, Upper Saddle River, NJ, 2001
3. Lawrence H. Van Vlack, Elements of Materials Science and Engineering, sixth
edition, Addison Wesley Longman, Inc. New York, 1998


Material Science

Associate Professor
India
Chapter 2. Atomic Structure, Interatomic Bonding and Structure

of Crystalline Solids
What is an atom and what is the unit used for their quantification?
What are atomic bonds and their impact on material behaviour?
What are crystal structures?
How to characterize a unit cell?
How do you represent crystal plan and directions?
What are Miller-Bravis indices?
What is anisotropy?
What is the impact of crystal structure on the material properties?
Does polymer has crystallinity?
Are the ceramics having crystalline structure?
What are silicates and what crystalline structure do they have?
Want to know how good you are in this chapter?
What is an atom and what is the unit used for their quantification?
Atoms are composed of electrons, protons, and neutrons. Electrons and protons
are negative and positive charged particles respectively. The mass of the electron is
negligible with respect to those of the proton and the neutron, which form the nucleus of
the atom. The unit of mass is an atomic mass unit (amu) = 1.66 × 10-27 kg, and equals
1/12 the mass of a carbon atom. The Carbon nucleus has Z=6, and A=6, where Z is the
number of protons, and A the number of neutrons. Neutrons and protons have very
similar masses, roughly equal to 1 amu each. A neutral atom has the same number of
electrons and protons, Z.

A mol is the amount of matter that has a mass in grams equal to the atomic mass in amu
of the atoms. Thus, a mole of carbon has a mass of 12 grams. The number of atoms in a
mole is called the Avogadro number, Nav = 6.023 × 1023. Note that Nav = 1 gram/1 amu.
Calculating n, the number of atoms per cm3 of a material of density δ (g/cm3):
δ
n = N av
M
where M is the atomic mass in amu (grams per mol). Thus, for graphite (carbon) with a
density δ = 1.8 g/cm3, M =12, we get 6 × 1023 atoms/mol × 1.8 g/cm3 / 12 g/mol) = 9 ×
1022 C atoms/cm3.
For a molecular solid like ice, one uses the molecular mass, M(H2O) = 18. With a density
of 1 g/cm3, one obtains n = 3.3 × 1022 H2O molecules/cm3. Note that since the water
molecule contains 3 atoms, this is equivalent to 9.9 × 1022 atoms/cm3.
Most solids have atomic densities around 6 × 1022 atoms/cm3. The cube root of that
number gives the number of atoms per centimeter, about 39 million. The mean distance
between atoms is the inverse of that, or 0.25 nm. This is an important number that gives
the scale of atomic structures in solids.
What are atomic bonds and their impact on material behaviour?
In order to understand the why materials behave like they do and why they differ in
properties, it is necessary that one should look at atomic level. The study primarily
concentrates on two issues: what made the atoms to cluster together, and how atoms are
arranged. As mentioned in earlier chapter, atoms are bound to each other by number of
bonds. These inter-atomic bonds are primarily of two kinds: Primary bonds and
Secondary bonds. Ionic, Covalent and Metallic bonds are relatively very strong, and
grouped as primary bonds, whereas van der Waals and hydrogen bonds are relatively
weak, and termed as secondary bonds. Metals and Ceramics are entirely held together by
primary bonds - the ionic and covalent bonds in ceramics, and the metallic and covalent
bonds in metals. Although much weaker than primary bonds, secondary bonds are still
very important. They provide the links between polymer molecules in polyethylene (and
other polymers) which make them solids. Without them, water would boil at -80˚C, and
life as we know it on earth would not exist.
Ionic Bonding: This bond exists between two atoms when one of the atoms is negative
(has an extra electron) and another is positive (has lost an electron). Then there is a
strong, direct Coulomb attraction. Basically ionic bonds are non-directional in nature. An
example is NaCl. In the molecule, there are more electrons around Cl, forming Cl- and
fewer electrons around Na, forming Na+. Ionic bonds are the strongest bonds. In real
solids, ionic bonding is usually exists along with covalent bonding.

Na Cl
Fig.1 Schematic representation of ioning bonding. Here, Na is giving an electron to Cl to

have stable structure
Covalent Bonding: In covalent bonding, electrons are shared between the atoms, to
saturate the valency. The simplest example is the H2 molecule, where the electrons spend
more time in between the nuclei of two atoms than outside, thus producing bonding.
Covalent bonds are stereo-specific 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. The hardness of diamond is a result of the fact
that each carbon atom is covalently bonded with four neighboring atoms, and each
neighbor is bonded with an equal number of atoms to form a rigid three-dimensional
structure.
H H
Figure 2. Schematic representation of covalent bond in Hydrogen molecule (sharing of

electrons)
Metallic Bonding: Metals are characterized by high thermal and electrical

conductivities. Thus, neither covalent nor ionic bondings are realized because both types
of bonding localize the valence electrons and preclude conduction. However, strong
bonding does occur in metals. The valence electrons of metals also are delocalized. Thus
metallic bonding can be viewed as metal containing a periodic structure of positive ions
surrounded by a sea of delocalized electrons. The attraction between the two provides the
bond, which is non-directional.
Electron cloud from

the valence electrons

M M M M
M M M M Core
M M M M
M M M M
Figure 3. Metallic bonding
Fluctuating Induced Dipole Bonds: Since the electrons may be on one side of the atom
or the other, a dipole is formed: the + nucleus at the center, and the electron outside.
Since the electron moves, the dipole fluctuates. This fluctuation in atom A produces a
fluctuating electric field that is felt by the electrons of an adjacent atom, B. Atom B then
polarizes so that its outer electrons are on the side of the atom closest to the + side (or
opposite to the – side) of the dipole in A.
Figure 4. Dipole bond in water
Polar Molecule-Induced Dipole Bonds: Another type of secondary bond exists with
asymmetric molecules, also called polar molecules because of positively and negatively
charged regions. A permanent dipole moment arises from net positive and negative
charges that are respectively associated with the hydrogen and chlorine ends of the
CH3Cl molecule, leading to bonding. The magnitude of this bond will be greater than for
fluctuating induced dipoles.

These two kinds of bonds are also called van der Waals bonds. Third type of secondary
bond is the hydrogen bond. It is categorized separately because it produces the strongest
forces of attraction in this category.
Permanent Dipole Bonds / Hydrogen bonding: It occurs between molecules as

covalently bonded hydrogen atoms – for example C-H, O-H, F-H – share single electron
with other atom essentially resulting in positively charged proton that is not shielded any
electrons. This highly positively charged end of the molecule is capable of strong
attractive force with the negative end of an adjacent molecule. The properties of water are
influenced significantly by the hydrogen bonds/bridges. The bridges are of sufficient
strength, and as a consequence water has the highest melting point of any molecule of its
size. Likewise, its heat of vaporization is very high.
What are crystal structures?
All metals, a major fraction of ceramics, and certain polymers acquire crystalline
form when solidify, i.e. in solid state atoms self-organize to form crystals. Crystals
possess a long-range order of atomic arrangement through repeated periodicity at regular
intervals in three dimensions of space. When the solid is not crystalline, it is called
amorphous. Examples of crystalline solids are metals, diamond and other precious stones,
ice, graphite. Examples of amorphous solids are glass, amorphous carbon (a-C),
amorphous Si, most plastics.
There is very large number of different crystal structures all having long-range
atomic order; these vary from relatively simple structures for metals to exceedingly
complex structures for ceramics and some polymers. To discuss crystalline structures it is
useful to consider atoms as being hard spheres, with well-defined radii. In this scheme,
the shortest distance between two like atoms is one diameter. In this context, use of terms
lattice and unit cell will be handy. Lattice is used to represent a three-dimensional
periodic array of points coinciding with atom positions. Unit cell is smallest repeatable
entity that can be used to completely represent a crystal structure. Thus it can be
considered that a unit cell is the building block of the crystal structure and defines the
crystal structure by virtue of its geometry and the atom positions within.
How to characterize a unit cell?
Unit cell is characterized by the following dimentions
• The type of atoms and their radii R.

• Cell dimensions (side a in cubic cells, side of base a and height c in HCP) in terms
of R.
• Angle between the axis α, β, γ

• a*, b*, c* - lattice distances in reciprocal lattice , α*, β*, γ* - angle in reciprocal
lattice
• n, number of atoms per unit cell. For an atom that is shared with m adjacent unit
cells, we only count a fraction of the atom, 1/m.
• CN, the coordination number, which is the number of closest neighbors to which
an atom is bonded.
• APF, the atomic packing factor, which is the fraction of the volume of the cell
actually occupied by the hard spheres. APF = Sum of atomic volumes/Volume of
cell.
Some very common crystal structures and relevant properties are listed in table 2.1.
Table 2.1: Common crystal structures and their properties.
Unit Cell n CN a/R APF
Simple Cubic 1 6 4/√4 0.52
Body-Centered Cubic 2 8 4/√ 3 0.68
Face-Centered Cubic 4 12 4/√ 2 0.74
Hexagonal Close Packed 6 12 0.74
Figure 2.1: Common metallic crystal structures.
How do you represent crystal plan and directions?
Miller indices:
It is understood that properties of materials depend on their crystal structure, and many of
these properties are directional in nature. For example: elastic modulus of BCC iron is
greater parallel to the body diagonal than it is to the cube edge. Thus it is necessary to
characterize the crystal to identify specific directions and planes. Specific methods are
employed to define crystal directions and crystal planes.

Methodology to define crystallographic directions in cubic crystal:
- a vector of convenient length is placed parallel to the required direction.

- the length of the vector projection on each of three axes are measured in unit cell
dimensions.
- these three numbers are made to smallest integer values, known as indices, by
multiplying or dividing by a common factor.
- the three indices are enclosed in square brackets, [uvw]. A family of directions is
represented by <uvw>.
Methodology to define crystallographic planes in cubic crystal:
- determine the intercepts of the plane along the crystallographic axes, in terms of
unit cell dimensions. If plane is passing through origin, there is a need to construct
a plane parallel to original plane.
- take the reciprocals of these intercept numbers.
- clear fractions.
- reduce to set of smallest integers.
- The three indices are enclosed in parenthesis, (hkl). A family of planes is
represented by {hkl}.
For example, if the x-, y-, and z- intercepts of a plane are 2, 1, and 3. The Miller indices
are calculated as:
- take reciprocals: 1/2, 1/1, 1/3.
- clear fractions (multiply by 6): 3, 6, 2.
- reduce to lowest terms (already there). => Miller indices of the plane are (362).
Figure 2.2 depicts Miller indices for number of directions and planes in a cubic crystal.
Figure 2.2: Miller indices in a cubic crystal.
Some useful conventions of Miller notation:

- If a plane is parallel to an axis, its intercept is at infinity and its Miller index will
be zero.
- If a plane has negative intercept, the negative number is denoted by a bar above
the number. Never alter negative numbers. For example, do not divide -1, -1, -1
by -1 to get 1,1,1. This implies symmetry that the crystal may not have!
- The crystal directions of a family are not necessarily parallel to each other.
Similarly, not all planes of a family are parallel to each other.
- By changing signs of all indices of a direction, we obtain opposite direction.
Similarly, by changing all signs of a plane, a plane at same distance in other side
of the origin can be obtained.
- Multiplying or dividing a Miller index by constant has no effect on the orientation
of the plane.
- The smaller the Miller index, more nearly parallel the plane to that axis, and vice
versa.
- When the integers used in the Miller indices contain more than one digit, the
indices must be separated by commas. E.g.: (3,10,13)
- By changing the signs of all the indices of (a) a direction, we obtain opposite
direction, and (b) a plane, we obtain a plane located at the same distance on the
other side of the origin.
More conventions applicable to cubic crystals only:
- [uvw] is normal to (hkl) if u = h, v = k, and w = l. E.g.: (111) ┴ [111].

- Inter-planar distance between family of planes {hkl} is given by:
a
d {hkl} =
h2 + k 2 + l 2
- [uvw] is parallel to (hkl) if hu + kv + lw = 0.

- Two planes (h1k1l1) and (h2k2l2) are normal if h1h2 + k1k2 + l1l2=0.
- Two directions (u1v1w1) and (u2v2w2) are normal if u1u2 + v1v2 + w1w2=0
- Angle between two planes is given by:
h1 h2 + k1 k 2 + l1l 2
cos θ =
h + k12 + l12 h22 + k 22 + l 22
1
2
The same equation applies for two directions.
Why Miller indices are calculated in that way?

- Using reciprocals spares us the complication of infinite intercepts.
- Formulas involving Miller indices are very similar to related formulas from
analytical geometry.

- Specifying dimensions in unit cell terms means that the same label can be applied
to any plane with a similar stacking pattern, regardless of the crystal class of the
crystal. Plane (111) always steps the same way regardless of crystal system.
What is Miller-Bravis indices?
Though Miller indices can describe all possible planes through any crystal, Miller-Bravis
indices are used in hexagonal crystal systems. This is because they reveal hexagonal
symmetry more clearly. Although partially redundant, they are used exclusively for
hexagonal systems.
Direction indices are obtained as above where first three indices are representative of
projections of the direction over three co-planar axes in the plane called basal plane while
the last index denotes the projection over the axis perpendicular to the basal plane.
Miller-Bravis indices for a plane are denoted as [uvtw], where t = -(u+v)
In the same procedure, planes in a hexagonal crystal are denoted by (hkil), where i = -
(h+k).
What is anisotropy?
It’s been agreed that many of the materials properties depend on the crystal structure.
However, crystals are not symmetric in all directions, or not the crystal planes same with
respect to atomic density/packing. Different directions in the crystal have different
packing. For instance, atoms along the edge of FCC crystals are more separated than
along its face diagonal. This causes properties to be different in different directions. This
directionality of properties is termed as Anisotropy.
Substances in which measured properties are independent of direction in which they are
measured are called isotropic. Though, in polycrystalline materials, the crystallographic
orientations of individual grains are random, specimen may behave isotropically.
What is the impact of crystal structure on the material properties?
Based on the nature of the crystallinity the materials are classified into Crystalline and
Non-crystalline materials.
Single Crystals: Crystals can be single crystals where the whole solid in sigle atomic
orientation.
Polycrystalline Materials: A solid can be composed of many crystalline grains, not

aligned with each other. It is called polycrystalline. The grains can be more or less
aligned with respect to each other. Where they meet is called a grain boundary.

Non-Crystalline Solids: In amorphous solids, there is no long-range order. But

amorphous does not mean random, since the distance between atoms cannot be smaller
than the size of the hard spheres. Also, in many cases there is some form of short-range
order. For instance, the tetragonal order of crystalline SiO2 (quartz) is still apparent in
amorphous SiO2 (silica glass).
Does polymer have crystallinity?
Crystallinity in polymers is more complex than in metals. Polymer molecules are often
partially crystalline (semicrystalline), with crystalline regions dispersed within
amorphous material. The degree of crystallinity may range from completely amorphous
to almost entirely crystalline; on the other hand metals are almost always crystalline
whereas ceramics are either completely crystalline or noncrystalline. The degree of
crystallinity of a polymer depends on cooling path, and also on chain configuration. For
copolymers, the more irregular and random the mer arrangement, the greater is
probability for noncrystalline nature. Crystalline polymers are denser than amorphous
polymers, so the degree of crystallinity can be obtained from the measurement of density.
Different models have been proposed to describe the arrangement of molecules in

semicrytalline polymers. In the fringed-micelle model, the crystallites (micelles) are
embedded in an amorphous matrix. Polymer single crystals grown are shaped in regular
platelets (lamellae). Spherulites are chain-folded crystallites in an amorphous matrix that
grow radially in spherical shape “grains”. These are considered to be the polymer
analogue of grains in polycrystalline metals and ceramics. Many semicrystalline
polymers form spherulites; each spherulite consists of a collection of ribbonlike chain-
folded lamellar crystallites that radiate outward from its center. E.g.: polyethelene, PVC.
A polymer’s response to mechanical forces under elevated temperatures is related to its

molecular structure. Based on this response, polymers are classified as: thermoplasts
(soften when heated and harden when cooled), and thermosets (become permanently hard
when heat is applied and do not soften upon subsequent heating). Thermosets are
generally harder and stronger than thermoplasts, and have better dimensional stability.
Most of the cross-linked and network polymers are thermosets; whereas linear and some
branched polymers are thermoplasts.
Are the ceramics have crystalline structure?
Yes, their crystal structures are generally more complex than those of metals. Ceramic
bonds are mixed, ionic and covalent, with a proportion that depends on the particular
ceramics. The ionic character is given by the difference of electronegativity between the
cations (+) and anions (-). Covalent bonds involve sharing of valence electrons. Very
ionic crystals usually involve cations which are alkalis or alkaline-earths (first two
columns of the periodic table) and oxygen or halogens as anions.
The building criteria for the ceramic crystal structure are as follows:

- maintain neutrality (charge balance dictates chemical formula)

- achieve closest packing
The crystal stability condition i.e. condition of minimum energy implies maximum
attraction and minimum repulsion. This leads to contact and configurations such that
anions have the highest number of cation neighbors (coordination number) and vice
versa. The coordination number is dependent on cation-anion radius ratio, which can be
determined from geometric relations. Table 2.2 presents relevant coordination numbers
and radius ratios.
Table 2.2. Co-ordination number dependency on cation-anion radius ratio.

Cation-anion
0.155 – 0.225 – 0.414 – 0.732 –
radius ratio < 0.155 > 1.000
0.225 0.414 0.732 1.000
(rc/ra)
Coordination
2 3 4 6 8 12
number
Figure-2.4 presents schematic arrangement of cations and anions with respective

coordinate positions for different radius ratios.
Figure 2.4: Ion arrangements for different coordination numbers.
Ceramic crystal structures
AX-type ceramic crystal structures: Most common ceramics are made of equal number of
cations and anions, and are referred to as AX compounds (A-cation, and X-anion). These
ceramics assume many different structures, named after a common material that
possesses the particular structure.
Rock salt structure: here the coordination number is 6, i.e. rc/ra = 0.414-0.732. This
structure can be viewed as an FCC of anions with cations occupying center of each edge

and the center of the cell. Thus it can be said that lattice is made of two interpenetrating
FCC lattices, one composed of cations, and the other of anions. E.g.: NaCl, MgO, FeO.
Cesium Chloride structure: here the coordination number is 8. Crystal structure consists
of anions at corners of a cube while a cation occupies the center, and vice versa. E.g.:
CsCl.
Zinc Blende structure: here the coordination number is 4. Unit cell is composed of one
kind of ions occupying corners and face centers of a cube, while the other kind of ions
occupies the interior tetrahedral positions. E.g.: ZnS, SiC.
AmXp- type structures: when the charges of cation and anions are not the same, to
maintain the neutrality, ceramic structures with chemical formula would exist. For
example – CaF2 with rc/ra = 0.8, and thus coordination number of 8. It can be expected
that crystal structure could be the same as that of CsCl. However cations are half many as
anions, thus only half the center positions are occupied. One unit cell shall be made of
eight cubes. E.g.: UO2, ThO2, PuO2.
AmBnXp-type structures: it is possible that ceramics do have more than one kind of
cations. E.g.: BaTiO3. unit cell is made of cube where Ba2+ ions occupies all eight
corners, T4+ occupies cube center, while O2- are at center of each face. This structure is
called perovskite crystal structure.
It is worth to understand and know more about some common most common ceramic in
nature. For example: silicates and carbon.
What are silicates and what crystalline structure do they have?
Oxygen and Silicon are the most abundant elements in Earth’s crust. Their combination
(silicates) occurs in rocks, soils, clays and sand. The bond is weekly ionic, with Si4+ as
the cation and O2- as the anion. However the bonds in silicates are strongly of covalent
character with strong directional Si-O bonds. Basic unit of silicates structures are thus is
SiO44- tetrahedron that consists of four oxygen atoms at corners of tetrahedron, and
silicon atom at the center of it. Various silicate structures consists SiO44- unit bonded in
1-, 2-, and 3- dimensions.
In silica (SiO2) every oxygen atom is shared by adjacent tetrahedra. Silica can either be
crystalline (e.g., quartz) or amorphous, as in glass. Crystalline forms of silica are known
to be complicated and comparatively open, thus of low densities compared with
amorphous glasses. Soda glasses melt at lower temperature than amorphous SiO2 because
the addition of Na2O (soda) that act as network modifier breaks the tetrahedral network.
Addition of intermediates such as Al2O3, TiO2 substitute of silicon atoms and become
part of stabilized network. Addition of network modifiers and intermediates lowers
melting point, and thus it is easy to form glass, for instance, bottles.

In complicated silicate structure, corner oxygen atom of basic unit is shared by other
tetrahedra, resulting in formulas such as SiO44-, Si2O76-, Si3O96-, etc. The repeating unit of
2-D sheet or layered structure is represented as Si2O52-. Such layered structures are
characteristics of clays and other minerals.
Want to know how good you are in this chapter?
1. Particles that most effects material properties
(a) Neutrons (b) Protons (c) Electrons (d) Valence electrons
2. Mean distance between atoms in the range of
(a) 25 nm (b) 2.5 nm (c) 0.25 nm (d) 0.025 nm
3. Which one of the following is not a strong bond?
(a) van der Waals bond (b) Covalent bond (c) Metallic bond (d) Ionic bond
4. Bond strength of secondary bonds is in the range of
(a) 1 kJ/mol (b) 10 kJ/mol (c) 100 kJ/mol (d) 1000 kJ/mol
5. Electron sea exists in
(a) Polar bonds (b) Ionic bond (c) Covalent bond (d) Metallic bond
6. Repeatable entity of a crystal structure is known as
(a) Crystal (b) Lattice (c) Unit cell (d) Miller indices
7. Coordination number for closest packed crystal structure
(a) 16 (b) 12 (c) 8 (d) 4
8. Atomic packing factor is

(a) Distance between two adjacent atoms (b) Projected area fraction of atoms on a
plane
(c) Volume fraction of atoms in cell (d) None
9. Coordination number in simple cubic crystal structure
(a) 1 (b) 2 (c) 3 (d) 4
10. The atomic diameter of an BCC crystal (if a is lattice parameter) is
(a) a (b) a/2 (c) a/(4/√3) (d) a/(4/√2)
11. A family of directions is represented by
(a) (hkl) (b) <uvw> (c) {hkl} (d) [uvw]
12. Miller indices for Octahedral plane in cubic crystal
(a) (100) (b) (110) (c) (111) (d) None
13. The plane (1⎯11) is parallel to
(a) (⎯11⎯1) (b) (⎯1⎯11) (c) (111) (d) (1⎯11)
14. The angle between [111] and [11⎯2] directions in a cubic crystal is (in degrees)
(a) 0 (b) 45 (c) 90 (d) 180
15. Miller indices of the line of intersection of (⎯1⎯11) and (110) are
(a) [110] (b) [101] (c) [10⎯1] (d) [⎯110]
16. Repeatable unit of polymers
(a) isomer (b) copolymer (c) homopolymer (d) mer

17. Pick the thermo-plast from the following
(a) Vinyls (b) Epoxies (c) Resins (d) Vulcanized rubber
18. For c coordination number of four, anion sits at the center of ……..where corners are
occupied by
cations
(a) Cube (b) Tetrahedron (c) Triangle (d) Octahedron
19. Layered silicate structures in clays consists the following group
(a) SiO44- (b) Si2O52- (c) Si2O76- (d) SiO44-
20. Schottky-defect in ceramic material is
(a) Interstitial impurity (b) Vacancy- interstitial pair of cations

(c) Pair of nearby cation and anion vacancies (d) Substitutional impurity
Answers:
1. d
2. c
3. a
4. b
5. d
6. c
7. b
8. c
9. b
10. c
11. b
12. c
13. a
14. c
15. d
16. d
17. a
18. b
19. b
20. c


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Material Sccience Prof. Satish V.

Prof. Satish V. Kailas

Chapter 2. Atomic Structure, Interatomic Bonding and Structure of

Indian Institute of Science Bangalore

Prof. Satish V. Kailas

Chapter 2. Atomic Structure, Interatomic Bonding and Structure of

Highlights, Motivation and Critical Concepts:

Indian Institute of Science Bangalore

Prof. Satish V. Kailas

Chapter 2. Atomic Structure, Interatomic Bonding and Structure

2.1 Atomic Structure and Atomic Bonding in Solids

2.1.1 Atomic Structure

Calculating n, the number of atoms per cm3 of a material of density δ (g/cm3):

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2.1.2 Atomic bonding in solids

Fig.1 Schematic representation of ioning bonding. Here, Na is giving an electron to Cl to

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Figure 2. Schematic representation of covalent bond in Hydrogen molecule (sharing of

Metallic Bonding: Metals are characterized by high thermal and electrical

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Figure 3. Metallic bonding

Figure 4. Dipole bond in water

Permanent Dipole Bonds / Hydrogen bonding: It occurs between molecules as

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2.2 Crystal Structures, Crystalline and Non-Crystalline materials

2.2.1 Crystal structures

Important properties of the unit cells are

• The type of atoms and their radii R.

Table 2.1: Common crystal structures and their properties.

Unit Cell n CN a/R APF

Simple Cubic 1 6 4/√4 0.52

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Body-Centered Cubic 2 8 4/√ 3 0.68

Face-Centered Cubic 4 12 4/√ 2 0.74

Hexagonal Close Packed 6 12 0.74

Figure 2.1: Common metallic crystal structures.

2.2.2 Crystalline and Non-crystalline materials

Polycrystalline Materials: A solid can be composed of many crystalline grains, not

Non-Crystalline Solids: In amorphous solids, there is no long-range order. But

2.3 Miller Indices, Anisotropy, and Elastic behavior of composites

2.3.1 Miller indices:

Methodology to define crystallographic directions in cubic crystal:

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- a vector of convenient length is placed parallel to the required direction.

Methodology to define crystallographic planes in cubic crystal:

Figure 2.2: Miller indices in a cubic crystal.

Some useful conventions of Miller notation:

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More conventions applicable to cubic crystals only:

- [uvw] is normal to (hkl) if u = h, v = k, and w = l. E.g.: (111) ┴ [111].

- [uvw] is parallel to (hkl) if hu + kv + lw = 0.

The same equation applies for two directions.

Why Miller indices are calculated in that way?

2.3.2 Miller-Bravis indices

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2.3.4 Elastic Behavior of Composites

A composite is defined as a artificially made muti-phase material, where constituent

Properties of composites depend on

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