JASHORE UNIVERSITY OF SCIENCE AND TECHNOLOGY (JUST)

IPE- 2203: Engineering Materials II (3 credit hours)

Dr. Md Mahfuzur Rahman

Assistant Professor, Dept. of IPE
19th July, 2022
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Course Syllabus
Course Contents

➢ Classification of Engineering Materials: metal, polymer, glasses, ceramics and

composites, their different properties

➢ Atomic Bonding: Different types of atomic bonding

➢ Structure of Solids: structure of solids, type of solids, crystal structure, different crystal
system, packing of atoms, Solidification process, defects in crystal system, solid state
defects, solid solution, insulator, Semiconductor

➢ Mechanical properties and Failure: Elastic and plastic behaviour of materials in

service: fracture, ductile-brittle transition, fatigue, creep, oxidation and degradation,
corrosion and corrosion protection

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Course Syllabus
Course Contents

➢ Phase diagram:

✓Unary phase diagram, Binary isomorphous system (Cu-Ni system),

Binary eutectic system (Cu-Ag system, Pb-Sn system)

✓Ternary phase diagram, determination of amount of phases and

compositions, development of microstructures, Gibbs phase rule.

✓The Fe-C equilibrium phase diagram, development of microstructures,

isothermal transformation diagram, continuous cooling transformation
diagram, mechanical behavior

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Course Syllabus
Course Contents

➢ Heat treatment processes of steel: annealing, normalizing, quenching, hardening,

tempering, different types of quenching media. Case hardening, carburizing and
nitriding, precipitation hardening/age hardening

➢ Production and uses, Melting furnaces: Bessemer and open hearth steel; Plain carbon
and different types of alloy steel, effects of alloying elements

✓Pig Iron: production and uses; Cast Iron: types, production, uses and effects of
impurities

➢ Powder Metallurgy, Bearing metals, light alloys common metals and their alloys,
Identification of metal

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Assessment Method

❖Assignments: 03(must be hand written and

submitted online)

❖Class Tests: 03 (Online)

❖At least one of the assignments will be

considered as a Class test.

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Why do we Study Materials?
Many an applied scientist or engineer, whether mechanical, civil, chemical, or electrical, will at one time or
another be exposed to a design problem involving materials.

A materials problem is one of selecting the right material from the thousands that are available. The final decision is
normally based on several criteria.

❖ First of all, the in-service conditions must be characterized, for these will dictate the properties required of
the material.

❖ A second selection consideration is any deterioration of material properties that may occur during service
operation. For example, significant reductions in mechanical strength may result from exposure to elevated
temperatures or corrosive environments.

❖ Finally, probably the overriding consideration is that of economics: What will the finished product cost? A
material may be found that has the ideal set of properties but is prohibitively expensive.

The more familiar an engineer or scientist is with the various characteristics and structure–property
relationships, as well as processing techniques of materials, the more proficient and confident he or she will be
in making judicious materials choices based on these criteria.

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Intended Learning Outcomes
ILO1: Identify the meaning an the Classification of Engineering Materials.
Engineering Materials

➢ The substances which are useful in the field of engineering are called Engineering materials.
➢ Materials of Engineering refers to selecting the correct materials for the application in which the
engineered part is being used.

Selection of Engineering Materials

✓ Primarily selected based on their mechanical, physical, chemical and manufacturing properties.
✓ The secondary points to be considered are the cost and availability, appearance, service life
and recyclability.
✓ In the present day, strict environmental legislations have forced the designers and engineers
to select the environment friendly materials which have minimum environmental impact.

Materials are often selected for their mechanical, physical, chemical and manufacturing properties for ensuring proper
functioning under desired conditions. When several materials are suitable for a particular design requirement, the
cheapest one is usually selected. 7
Classification of Engineering Materials

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Metals

Metals
➢ Materials in this group are composed of one or more metallic elements (e.g., iron,
aluminum, copper, titanium, gold, and nickel), and often also nonmetallic elements (e.g.,
carbon, nitrogen, and oxygen) in relatively small amounts.

➢ Atoms in metals and their alloys are arranged in a very orderly manner, and in comparison
to the ceramics and polymers, are relatively dense.

Properties
➢ Relatively stiff and strong, yet are ductile, and are resistant to fracture

➢ Metallic materials have large numbers of nonlocalized electrons; that is, these electrons are
not bound to particular atoms. Thus, metals are extremely good conductors of electricity
and heat
➢ Metals are not transparent to visible light; a polished metal surface has a lustrous
appearance.
➢ Some of the metals (i.e., Fe, Co, and Ni) have desirable magnetic properties. 9
Ceramics
Ceramics
➢ Ceramics are compounds between metallic and nonmetallic elements; they are most frequently oxides,
nitrides, and carbides.

➢ Examples, aluminum oxide (or alumina, Al2O3), silicon dioxide (or silica, SiO2), silicon carbide (SiC), silicon
nitride (Si3N), and, in addition, what some refer to as the traditional ceramics—those composed of clay
minerals (i.e., porcelain), as well as cement and glass.

Properties
✓ Relatively stiff and strong—stiffnesses and strengths are comparable to those of the metals.
✓ They are typically very hard.
✓ Ceramics brittle (lack of ductility) and are highly susceptible to fracture.

✓ 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.
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Polymers
Polymers
➢ Polymers include the familiar plastic and rubber materials. Many of them are organic compounds that are
chemically based on carbon, hydrogen, and other nonmetallic elements (i.e., O, N, and Si).
➢ They have very large molecular structures, often chainlike in nature, that often have a backbone of carbon
atoms.
➢ Examples: polyethylene (PE), nylon, poly(vinyl chloride) (PVC), polycarbonate (PC), polystyrene (PS), and
silicone rubber.

Properties
✓ These materials typically have low densities.
✓ They are not as stiff nor as strong as metals.
✓ Polymers are extremely ductile and pliable (i.e., plastic), which means they are easily formed into complex
shapes.
✓ Relatively inert chemically and unreactive in a large number of environments.
✓ One major drawback to the polymers is their tendency to soften and/or decompose at modest
temperatures, which, in some instances, limits their use.
✓ They have low electrical conductivities and are nonmagnetic.

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Composites
Composites
➢ A composite is composed of two (or more) individual materials, which come from the categories
previously discussed—metals, ceramics, and polymers.
➢ 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.

➢ Naturally composites: wood and bone.

➢ Synthetic composites: fiberglass, in which small glass fibers are embedded within a polymeric material
(normally an epoxy or polyester).
✓ The glass fibers are relatively strong and stiff (but also brittle), whereas the polymer is more flexible.
Thus, fiberglass is relatively stiff, strong, and flexible. In addition, it has a low density.
✓ Carbon fiber–reinforced polymer (CFRP) composite—carbon fibers that are embedded within a
polymer.
✓ These materials are stiffer and stronger than glass fiber–reinforced materials, but more expensive.
CFRP composites are used in some aircraft and aerospace applications, as well as high-tech sporting
equipment (e.g., bicycles, golf clubs, tennis rackets, and skis/snowboards) and recently in automobile
bumpers. The new Boeing 787 fuselage is primarily made from such CFRP composites.

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Behaviour and the manufacturing properties of materials

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Properties of Engineering Materials
ILO2: Identify different properties of materials and describe the importance of learning those.
i. General Physical Properties
➢ Density: It is defined as the ratio of an objects mass to its volume.
– Density is a function of the mass of the atoms making up the materials and the distance between them.
Closely packed atoms characterize high density materials such as Tungsten or Neptunium. In contrast
light, relatively distant atoms compose low density materials such as Beryllium or Aluminum.
➢ Availability/Manufacturability
– The importance of a material being available is obvious. Materials which are not available cannot be
used. Any other desirable qualities are useless if a material cannot be processed into the shape required
to perform its function.
➢ Cost
– A materials cost is also generally a limiting factor. Understanding the entire processing
sequence is critical to accurately evaluating the true cost of a material.
➢ Appearance

- Because the appearance of many mechanical components seems fairly trivial it is also easy to
overlook its importance in the marketing and commercial success of a product. 14
Properties of Engineering Materials

ILO2: Identify different properties of materials and describe the importance of learning
those.
ii. Mechanical Properties
– Strength-ability of a material to resist the application of load without rupture.
– Hardness-ability of a material to resist penetration or scratching.
– Hardenability-ability of a material to be hardened by heat treatment.
– Toughness-property of a material where it can absorb energy before actual fracture.
– Brittleness-ability of material to fracture on receiving shock or blow.
– Ductility-ability of a material to be drawn into wires.
– Creep -ability of a material to flow like a viscous liquid under the application of stress and
temperature is called creep. The phenomenon where deformation stops even if the load is
acting.
– Resilience-property of a material to absorb energy within elastic range. This required for
springing action.
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Mechanical Properties
• Creep is the permanent elongation of a component under a static load maintained for a period of
time. This phenomenon occurs in metals and certain nonmetallic materials, such as thermoplastics and
rubbers, and it can occur at any temperature; lead, for example, creeps under a constant tensile load at
room temperature. However, for metals and their alloys, creep of any significance occurs at elevated
temperatures, beginning at about 200°C (400°F) for aluminum alloys and at about 1500°C
(2800°F) for refractory alloys. The mechanism of creep at elevated temperature in metals is generally
attributed to grain-boundary sliding.
• Stress Relaxation. Stress relaxation is closely related to creep. In stress relaxation, the stresses
resulting from loading of a structural component decrease in magnitude over a period of time, even
though the dimensions of the component remain constant. An example is the decrease in tensile stress
of a wire in tension between two fixed ends (as in the wires in a piano); other examples include stress
relaxation in rivets, bolts, guy wires, and similar parts under either tension, compression, or flexure.
Stress relaxation is particularly common and important in thermoplastics. Stress relaxation, like creep,
is a consequence of the viscoelastic behavior of the polymer. A reduction of the stress acting on a
material over a period of time at a constant strain due to viscoelastic deformation.
• Perhaps the most familiar example of this behavior is a rubber band (an elastomer) stretched around a
pile of books. Initially, the tension in the rubber band is high when the rubber band is taut. After
several weeks, the strain in the rubber band is unchanged (it still completely encircles the books), but
the stress will have decreased. Similarly, the nylon strings in tennis rackets are pulled at a higher
tension initially since this tension (i.e., stress) decreases with time. 16
 Properties of Engineering Materials

ILO2: Identify different properties of materials and describe the importance of learning
those.
iii. Thermal Properties
➢ Thermal conductivity: The thermal conductivity is the rate of heat transfer through a material in steady state.
➢ Thermal diffusivity : The thermal diffusivity is a measure of the transient heat flow through a material.
➢ Specific heat: The specific heat is a measure of the amount of energy required to change the temperature of a given mass of
material. Specific heat is measured by calorimetry techniques and is usually reported both as CV, the specific heat measured at
constant pressure, or CP, the specific heat measured at constant pressure.
➢ Melting point: The melting point is the temperature at which a material goes from the solid to the liquid state at one
atmosphere.
➢ Glass transition temperature: The glass transition temperature, or Tg is an important property of polymers. The glass
transition temperature is a temperature range which marks a change in mechanical behavior. Above the glass transition
temperature a polymer will behave like a ductile solid or highly viscous liquid. Below Tg the material will behave as a brittle
solid.
➢ Creep resistance : Creep is slow, temperature aided, time dependent deformation. Creep is typically a factor in materials
above one third of their absolute melting temperature or two thirds of their glass transition temperature. Creep resistance is
an important material property in high temperature design, but it is difficult to quantify with a single value. Creep response is
a function of many material and external variables, including stress and temperature. Often other environmental factors such
as oxidation or corrosion play a role in the fracture process.
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Properties of Engineering Materials
iv. Electrical and magnetic
➢ Resistivity
➢ Dielectric constant
➢ Magnetic permeability
v. Environmental interaction
➢ Oxidation
➢ Corrosion
➢ Wear

vi. Production
➢ Ease of manufacture
➢ Joining
➢ Finishing

vii. Aesthetic
➢ Color
➢ Texture
➢ Feel 18
 Atomic Structure & Bonding
ILO3: Describe Atomic structure & Bonding forces and Energies
Atomic Structure
(Elementary particles, electronic distribution and atomic size/structure)

❖ Each atom consists of a very small nucleus composed of protons and neutrons, which is
encircled by moving electrons.

❖ Both electrons and protons are electrically charged, the charge magnitude being 1.6 × 10−19 C,
which is negative in sign for electrons and positive for protons; neutrons are electrically neutral.
Masses for these subatomic particles are infinitesimally small; protons and neutrons have
approximately the same mass, 1.67 × 10−27 kg, which is significantly larger than that of an
electron, 9.11 × 10−31 kg.

❖ Each chemical element is characterized by the number of protons in the nucleus, or the atomic
number (Z). For an electrically neutral or complete atom, the atomic number also equals the
number of electrons. This atomic number ranges in integral units from 1 for hydrogen to 92 for
uranium, the highest of the naturally occurring elements.

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 Atomic Structure & Bonding
ILO3: Describe Atomic structure & bonding forces and Energies.

Bonding Forces and Energies

❖ Perhaps the principles of atomic bonding are best illustrated by considering how two isolated atoms
interact as they are brought close together from an infinite separation.

❖ At large distances, interactions are negligible, because the atoms are too far apart to have an
influence on each other; however, at small separation distances, each atom exerts forces on the
other.
Attractive force is due to electrostatic
attraction between electrons of one
❖ These forces are of two types: atom and the nucleus of the other.
✓ Attractive (FA)
✓ and Repulsive (FR)

The magnitude of each depends on the

separation or interatomic distance (r).

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 Atomic Structure & Bonding
ILO3: Describe Atomic structure & bonding Forces and Energies.
Dependence of bonding forces and energies on interatomic
separation
When atoms of a metal approach each other, two opposing forces influence the internal
energy, an attractive force between the electrons and both positive nuclei (FA), and a repulsive
force between the positive nuclei and also between the electrons (FR).

✓ The FA tends to decrease the internal energy and the FR tends to increase it.
✓ At some distance these two forces will just balance each other and the total internal
energy E, will be a minimum, corresponding to an equilibrium condition.
✓ The equilibrium distance ro is different for each element and is determined by
measuring the distance of closest approach of atoms in the solid state.
✓ If the atoms are visualized as spheres just touching at equilibrium, then the distance
between centers of the spheres may be taken as the approximate atomic diameter.
✓ The atomic diameter increases as the number of occupied shells increases and
decreases as the number of valence electrons increases.
.

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Atomic Structure & Bonding
ILO3: Describe Atomic structure & bonding Forces and Energies.
Dependence of bonding forces and energies on interatomic separation.

✓ The net force FN is:

𝐹𝑁 = 𝐹𝐴 + 𝐹𝑅
which is also a function of the interatomic separation.
✓ When FA and FR balance, or become equal, there is no net force i.e.
𝐹𝑁 = 𝐹𝐴 + 𝐹𝑅 = 0 and a state of equilibrium exists.
✓ The centers of the two atoms will remain separated by the
equilibrium spacing r0, as indicated in Figure. For many atoms, r is
approximately 0.3 nm.
✓ Mathematically, energy (E) and force (F) are related as, 𝐸 = ‫𝑟𝑑 𝐹 ׬‬.
𝑟 𝑟
✓ For atomic system, net energy, 𝐸𝑁 = ‫ 𝑟𝑑 𝐴𝐹 ∞׬‬+ ‫ 𝐴𝐸 = 𝑟𝑑 𝑅𝐹 ∞׬‬+
𝐸𝑅 .

✓ The minimum in the net energy curve corresponds to the equilibrium

spacing, r0. Furthermore, the bonding energy for these two atoms, E0,
corresponds to the energy at this minimum point; it represents the energy
that would be required to separate these two atoms to an infinite
separation.

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 Atomic Structure & Bonding
ILO4: Explain different types of primary and secondary bonds that are found in solids
Primary Bonds
➢ Primary bonds, also known as “strong bonds,” are created when there is direct interaction of electrons
between two or more atoms, either through transfer or as a result of sharing. The more electrons per atom
that take place in this process, the higher the bond “order” (e.g., single, double, or triple bond) and the
stronger the connection between atoms.

➢ There are four general categories of primary bonds: (i) Ionic, (ii) covalent, (iii) polar covalent, and (iv) Metallic
bond.

❖ For ionic bonds, electrically charged ions are formed by the transference of valence electrons from one atom
type to another. This type of bonding is found in ceramic materials.
❖ There is a sharing of valence electrons between adjacent atoms when bonding is covalent. Polymers and some
ceramic materials covalently bond.
❖ The percent ionic character (%IC) of a bond between two elements (A and B) depends on their electro-
negativities (X’s).
❖ With metallic bonding, the valence electrons form a “sea of electrons” that is uniformly dispersed around the
metal ion cores and acts as a form of glue for them. Metallic materials exhibit this type of bonding.

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 Atomic Structure & Bonding
ILO4: Explain different types of primary and secondary bonds that are found in solids

Secondary Bonds

➢ Secondary bonds, or weak bonds, occur due to indirect interaction of electrons in adjacent atoms or
molecules.

➢ There are three main types of secondary bonding: hydrogen bonding, dipole–dipole interactions, and
van der Waals forces.

➢ For hydrogen bonding, highly polar molecules form when hydrogen covalently bonds to a
nonmetallic element such as fluorine.

➢ The Van der Waals forces arise due to momentary electric dipoles (regions of positive and
negative charge) that can occur in all atoms and molecules due to statistical variations in the
charge density. These intermolecular forces are common, but very weak, and are found in inert
gases where other types of bonding do not exist.
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Atomic Structure & Bonding
Ionic Bonds

❖ An element like sodium with one excess electron will readily give it up so that it has a completely
filled outer shell.
❖ It will then have more protons than electrons and become a positive ion (charged atom) with a +1
charge. An atom of chlorine, on the other hand, with seven electrons in its outer shell, would like
to accept one electron and become a negative ion with a -1 charge.

❖ When sodium and chlorine atoms are placed together, there is a transfer of electrons from the
sodium to the chlorine atoms, resulting in a strong electrostatic attraction between the Na+ and
Cl- ions and forming the compound sodium chloride.

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Atomic Structure & Bonding
Covalent Bonds

Atoms of some elements may attain a stable electron structure by sharing one or more electrons
with adjacent atoms. Nitrogen (atomic number 7) has 5 electrons in the outer shell and needs 3
more to complete that shell.

A nitrogen atom shares the electrons of three hydrogen atoms and in turn shares three of its
electrons with the three hydrogen atoms to form the compound ammonia (NH3).

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Atomic Structure & Bonding
Metallic Bonds

Each of the atoms of the metal contributes its valence electrons to the formation of a negative electron
"cloud." These electrons are not associated with a particular ion but are free to move among the positive
metallic ions in definite energy levels.

The metallic ions are held together by virtue of their mutual attraction for the negative electron cloud.

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Atomic Structure & Bonding
Effect of bond energy on the materials properties

A number of material properties depend on E0, the curve shape, and bonding type.

For example, materials having large bonding energies typically also have high melting temperatures; at room
temperature, solid substances are formed for large bonding energies, whereas for small energies the gaseous state is
favored; liquids prevail when the energies are of intermediate magnitude.

✓ The slope for a relatively stiff material

at the r = r0 position on the curve
will be quite steep.

✓ The slopes are shallower for more

flexible materials.

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Atomic Structure & Bonding
Effect of bond energy on the materials properties

Thermal properties

➢ A deep and narrow “trough,” which typically occurs for materials having large bonding energies, normally
correlates with a low coefficient of thermal expansion and relatively small dimensional alterations for changes in
temperature.

✓ Thermal expansion is really due to the

asymmetric curvature of this potential
energy trough, rather than the increased
atomic vibrational amplitudes with rising
temperature.

✓ If the potential energy curve were

symmetric, there would be no net change
in interatomic separation and,
consequently, no thermal expansion.

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Metal Structure
Atomic Diameter

➢ When atoms of a metal approach each other, two opposing forces

influence the internal energy.
➢ The an attractive force between the electrons and both positive nuclei
tends to decrease the internal energy.
➢ The a repulsive force between the positive nuclei and also between the
electrons tends to increase internal energy.
➢ At some distance these two forces will just balance each other and the
total internal energy E, will be a minimum, corresponding to an equilibrium
condition.

➢ If the atoms are visualized as spheres just touching at equilibrium, then the
distance between centers of the spheres may be taken as the
approximate atomic diameter.
➢ The atomic diameter increases as the number of occupied shells increases
and decreases as the number of valence electrons increases.

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Metal Structure

Macrostructure
➢ Some structural elements are of macroscopic dimensions, that is, are large enough to be observed with the
unaided eye.

➢ For example, the shape and average size or diameter of the grains for a polycrystalline specimen are
important structural characteristics.

➢ Macroscopic grains are often evident on aluminum streetlight posts and also on garbage cans. Relatively large
grains having different textures are clearly visible on the surface of the sectioned lead ingot.
➢ Macrostructure of material is the external appearance of material which is due to the internal symmetry of
crystals forming it.

➢ Length of scale for this level is approximately greater than 1000 nm at which features like porosity, surface
coatings, internal or external cracks, fractured surfaces slag inclusions, materials' flow lines, segregation, heat
affected zone, etc. can be observed.

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Metal Structure

Microstructure
❖ Microstructure is a larger scale than the atomic level definition.

❖ In most materials the constituent grains are of microscopic dimensions, having diameters that may be on the
order of microns, and their details must be investigated using some type of microscope.

❖ Grain size and shape are only two features of what is termed the microstructure.

❖ Microstructure is subject to direct microscopic observation, using optical or electron microscopes.

❖ In metal alloys, microstructure is characterized by the number of phases present, their proportions, and
the manner in which they are distributed or arranged. The microstructure of an alloy depends on such
variables as the alloying elements present, their concentrations, and the heat treatment of the alloy (i.e.,
the temperature, the heating time at temperature, and the rate of cooling to room temperature).

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Metal Structure

Substructure

❖ This refers to the structure obtained by using a microscope with much higher magnification and
resolution than the optical one.

❖ In an electron microscope a magnification of 106 times the linear is possible. Here, due to the
very small wavelength of electrons compared to visible light, the resolving power also increases
so that much finer details is shown up.

❖ With the help of electron microscope, one can get information on very fine particles or crystal
imperfection like dislocations. The length of the scale is considered as up to 1010m.

❖ By study of substructure one can understand processes/phenomena occurring at such a small scale.

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Metal Structure

Crystal Structure

➢ In crystallography, crystal structure is a description of the ordered arrangement of atoms,

ions or molecules in a crystalline material.

➢ Ordered structures occur from the intrinsic nature of the constituent particles to form
symmetric patterns that repeat along the principal directions of three-dimensional space in
matter.

➢ i.e. the crystal structure of the material is the manner in which atoms, ions, or molecules are
spatially arranged.

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Metal Structure
➢ Since atoms tend to assume relatively fixed positions, this gives rise
to the formation of crystals in the solid state.

➢ The atoms oscillate about fixed locations and are in dynamic

equilibrium rather than statically fixed.

➢ The three-dimensional network of imaginary lines connecting the atoms

is called the space lattice, while the smallest unit having the full
symmetry of the crystal is called the unit cell.

➢ The specific unit cell for each metal is defined by its parameters, which
are the edges of the unit cell a, b, c and the angles α (between b and c),
β (between a and c), and γ (between a and b).

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 Metal Structure
✓ There are only 14 possible types of space lattices, and they fall into
seven crystal systems.

✓ Fortunately, most of the important metals crystallize in either the

cubic or hexagonal systems,

✓ Only three types of space lattices are commonly encountered: the

b.c.c. (body-centered cubic), the f.c.c. (face-centered cubic), and the
c.p.h. (close-packed hexagonal).
HCP

BCC FCC 36
Metal Structure

37
Crystallization
❖ Crystallization is the (natural or
artificial) process by which a solid
forms, where the atoms or molecules
are highly organized into a structure
known as a crystal. Some of the ways
by which crystals form are
precipitating from a solution, freezing,
or more rarely deposition directly
from a gas.
❖ Attributes of the resulting crystal
depend largely on factors such as
temperature, air pressure, and in the
case of liquid crystals, time of fluid
evaporation.
➢ Crystallization occurs in two major
steps.
➢ The first is nucleation, the appearance
of a crystalline phase from either a
supercooled liquid or a supersaturated
solvent.
➢ The second step is known as crystal
growth, which is the increase in the
size of particles and leads to a crystal
state. An important feature of this step
is that loose particles form layers at
the crystal's surface lodge themselves
into open inconsistencies such as
pores, cracks, etc.
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Mechanism of crystallization
➢ Crystallization is the transition from the liquid to the solid state and
occurs in two stages:
I. Nuclei formation
II. Crystal growth

The atoms in the solid are much closer, together, so that

solidification occurs with a release of energy. This difference in
potential energy between the liquid and solid states is known as the
latent heat of fusion. However, energy is required to establish a
surface between the solid and liquid. In pure materials, at the
freezing point, sufficient energy is released by the heat of fusion to
create a stable boundary, and some undercooling is always necessary
to form stable nuclei.

Schematic diagram of structures of (a) crystal and (b) liquid. Area ABCDE in liquid is identical in arrangem
as in crystal. 39
Mechanism of crystallization
When the temperature of the liquid metal has dropped sufficiently below its freezing point, stable aggregates or
nuclei appear spontaneously at various points in the liquid. These nuclei, which have now solidified, act as centers
for further crystallization.

As cooling continues, more atoms tend to freeze, and they may attach themselves to already existing nuclei or
form new nuclei of their own.

Each nucleus grows by the attraction of, atoms from the liquid into its space lattice. Crystal growth continues in
three dimensions, the atoms attaching themselves in certain preferred directions, usually along the axes of the
crystal.

This gives rise to a characteristic treelike structure which is called a dendrite. Since each nucleus is formed by
chance, the crystal axes are pointed at random and the dendrites growing from them will grow in different
directions in each crystal.

40
Mechanism of crystallization
➢ Finally, as the amount of liquid decreases, the
gaps between the arms of the dendrite will be
filled and the growth of the dendrite will be
mutually obstructed by that of its neighbors.
This leads to a very irregular external shape.

➢ The crystals found in all commercial metals are

commonly called grains because of this variation
in external shape. The area along which crystals
meet known as the grain boundary which is a
region of mismatch.
➢ This leads to a non-crystalline (amorphous)
structure at the grain boundary with the atoms
irregularly spaced.
➢ Since the last liquid to solidify is generally along
the grain boundaries, there tends to be a higher
concentration of impurity atoms in that area.

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 Atomic Bonding
❑ The mechanisms of bonding between the atoms are based on the
foregoing discussion on electrostatic interatomic interaction.

❑ The types of bond and bond strength are determined by the electronic
structures of the atoms involved.
❑ The valence electrons take part in bonding. The atoms involved
acquire, loose or share valence electrons to achieve the lowest
energy or stable configuration of noble gases.
❑ Atomic bonding can be broadly classified as
❖ i) primary bonding
❖ ii) secondary bonding

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 Atomic Bonding
Primary Bonds

Three types primary bonds are found in solids:

❖ Ionic
❖ Covalent
❖ Metallic

Majority of the engineering materials consists of one of these bonds.

Many properties of the materials depend on the specific kind of bond
and the bond energy,

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 Ionic Bond
Ionic bonds are generally found in compounds composed of
metal and non-metal and arise out of electrostatic attraction
between oppositely charged atoms (ions).

Number of electron in outer shell is 1 in Na and 7 in Cl .

Therefore, Na will tend to reject one electron to get stable
configuration of Ne and Cl will accept one electron to obtain
Ar configuration. The columbic attraction between Na+ and
Cl¯ions thus formed will make an ionic bond to produce NaCl.
Some other examples are CaF2, CsCl , MgO, Al2O3.

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 Covalent Bond
In this type of bonding, atoms share their valence electrons
to get a stable configuration.
Methane (CH4): Four hydrogen atoms share their valence
electrons with one carbon atom and the carbon atom in turn
shares one valence electron with each of the four hydrogen
atoms. In the process both H and C atoms get stable
configuration and form a covalent bond.

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 Covalent bond

Covalent bonds are formed between atoms of similar

electronegativity.

C atoms in diamond are covalently bonded to each other.

Si also has valency of four and forms SiC through

covalent bonding with C atoms.

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 Metallic Bond
In metals the valence electrons are not really bound to one
particular atom, instead they form a sea or cloud of valence
electrons which are shared by all the atoms. The remaining
electrons and the nuclei form what is called the ion core
which is positively charged. The metallic bond arises out of
the columbic attraction between these two oppositely
charged species – the electron cloud and the ion cores.

Electrons
sea
Ion core

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 Characteristics of primary bonds
Structure-property correlation
➢ Ionic and covalent bonds posses high bond energy 450 –1000
kJ/mole
➢ High bond strength in ionic and covalent solids results in high
melting point, high strength and hardness. e.g. diamond
➢ As the electrons are tightly bound to the atoms they are
generally poor conductors of heat and electricity and are
brittle in nature
➢ Most of the ceramics consist of covalent (SiC) or ionic bonds
(Al2O3) or a mix of both and hence, exhibit all the properties
described above

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 Structure-property correlation
Metallic bonds on the other hand provide good thermal and
electrical conductivities as the valence electrons are free to
move.
The metallic bond energy is 68 kJ/mol (Hg) on the lower
side and 850 kJ/mol (W, tungsten) on the higher side.
Bond strength increases with atomic number as more
electrons are available to form the bonds with the ion cores.
As a result melting point, hardness and strength increases
with atomic number.
Metals are ductile as the free moving electrons provides
agility to the bonds and allows plastic deformation.

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 Secondary Bonds
Van der Waals bonding
Van der Waals bonding between molecules or atoms arise
due to weak attraction forces between dipoles

The natural oscillation of atoms leading to momentary

break down of charge symmetry can generate temporary
dipoles

Dipoles can induce dipoles and attraction between

opposites ends of the dipoles leads to weak bonding

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 Van der Waals Bonding

An ion can also induce a dipole

Some molecules like HCl have permanent dipoles due

to asymmetrical arrangement of +ve and –ve charges.

Van der Waals bonding is much weaker compared to

primary bonds. Bond energy lies in the range of 2 – 10
kJ/mol.

Molecules in liquid and gas are held by weak Van der

Waals forces

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 Van der Waals bonds
The atomic layers in graphite are held together by weak
van der Waals bonds. Therefore, the layers can move easily
over each other and this imparts the lubricating property
graphite is known for.

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 Hydrogen bonding
Hydrogen bond is a type of secondary bond found in
molecules containing hydrogen as a constituent.
The bond originates from electrostatic interaction between
hydrogen and another atom of high electronegativity such
as fluorine or oxygen.
The strength of hydrogen bonds is in the range of 10 - 50
kJ/mol.
Water molecules, for example, are connected by hydrogen
bonds (dashed lines in the picture).

H2O

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