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DEPARTMENT OF MECHANICAL ENGINEERING

Subject: ENGINEERING MATERIALS AND


METALLURGY
Subject Code: MET 204

Module Handouts
Prepping and delivering Lecturer: Eng. Alexis MUHIRWA

Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering Dpt.;


Academic year: 2015-2016; Subject: Engineering materials and metallurgy
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RECOMMENDED TEXTBOOKS
R K Singal, Mridul Singal; Basics of Mechanical Engineering; 2007
Chandra P. Sharma, Engineering Materials: Properties and Applications of Metals and Alloys, 2004
Engineering Materials: properties and Selection; Author: Kenneth G. Budinski, Prentice Hall of India, 5th
Ed. 1998.
Kenneth G. Budinski and Michael K. Budinski, Engineering Materials: Properties and Selection, 2009; 9th
Edition
William D. Callister; Jr. John Wiley & Sons, Materials Science and Engineering - An Introduction; 2003.
Lawrence H. Van Vlack; Elements of Materials Science and Engineering; Addison-Wesley 1989.
John Schey Hardcover; Introduction to Manufacturing Processes; 1999
Peter J. Shull; Nondestructive Evaluation: Theory, Techniques, and Applications (Mechanical
Engineering); 2002
R.L. Timings; Engineering materials Vol1 and Vol 2; Longman 1989.
Norman E. Dowling, Mechanical Behavior of Materials, 2012, 4th Edition
B.S. Narang, Materials Science; CBS Publications, 1991 edition.
William D. Callister; Fundamentals of Materials Science and Engineering: An Integrated Approach, 2004
E.T.N. Bisanda, Introductory materials science Students reader, 2003.
D R H Jones and Michael F. Ashby; An Introduction to Properties, Applications and Design, 2011; Fourth
Edition
V. Raghavan, Materials Science and Engineering; Prentice Hall of India, 1999.
Vernon John, Introduction to Engineering Materials; Palgrave Macmillan, 2003.
K.M. Gupta, Materials Science and Engineering; Umesh Publishers, 2001.
Carl A. Keyser, Material Science in Engineering, CBS Publishers, 1989.
William D. Callister Jr. and David G. Rethwisch, Materials Science and Engineering: An Introduction, 2009,
8th Edition
Kenneth G. Budinsk, Michael K. Budinski; Engineering Materials: Properties and Selection (8th Edition),
2004
Richard W. Hertzberg, Richard P. Vinci; Deformation and Fracture Mechanics of Engineering Materials,
2012
Joachim Roesler, Harald Harders; Mechanical Behaviour of Engineering Materials: Metals, Ceramics,
Polymers, and Composites, 2007

Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering Dpt.;


Academic year: 2015-2016; Subject: Engineering materials and metallurgy
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0.0 INTRODUCTION TO ENGINEERING MATERIALS STRUCTURE


Materials have been at the base of all innovations in all human endeavors to better his life. Innovation
in engineering often means the clever use of a new material for a specific application. For example:
plastic containers replaced age-old metallic containers. Harnessed materials in production of various
items have been increasingly improved from generation to generation. Thence; the civilization that
indeed is connected to the development was named by historians according to the discovery of most
significant materials that changed human lives; notably:
- Stone Age (natural materials like stone, clay, skin, and wood)
- Bronze Age (3000BC when people found copper and developed its hardened alloy)
- the Iron Age (its abundance and availability brought tools and utensils)
- Steel Age (1200BC but cheap processes to produce steel are dated around 1850 AC and came up
with railroads, instruments, and the Industrial Revolution)
- Space Age (stronger and light materials like composites electronic materials like semiconductors
and other electronic gadgets, reason why it is contemporaneous with the Electronic Age).
Grounds of Engineering materials as a subject: Engineering disasters are frequently linked to the
misuse of materials. So it is tremendously vital that the professional engineer should know how to
select materials which best fit the demands of the design - economic and aesthetic demands, as well as
demands of strength and durability. Hence, we can outsource the following objectives:
To understand inherent characteristic limits of materials and the gradual or abrupt change of
their individual properties with use.
To comprehend reasons behind materials behaviors/properties from their structure at atomic
scale.
To seize most influential production processes that are involved in synthetic materials
manufacture
To grasp involved procedures in new material creation that might possess desirable properties
for certain working conditions.
To ascertain the consistency of the material by testing methods prior or along materials
exploitation
To be familiar with the use of materials well-chosen for different properties-depend
applications.
To carry out an auspicious selection of material for a given use by a decent screening out based
on cost and performance.
Materials are distinguished by their individual behaviors/properties. Some are found in nature and
others are man-made developments; they are well understood from their basic tiny atomic structure.

Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering Dpt.;


Academic year: 2015-2016; Subject: Engineering materials and metallurgy
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0.1 Atomic structure warm-up


0.1.1 Basic definitions
All matter is considered to be composed of unit substances known as chemical elements. These are the
smallest units that are distinguishable on the basis of their chemical activity and physical properties. The
elements are composed of atoms which have distinct structure characteristic of each element. Here are
some definitions:
Matter: Anything that has weight and that takes up space.
Forms/states of Matter: Solid, Liquid, Gas
Molecule: The smallest particle of matter that retains the same properties of that matter. Example:
Water H2O = H2 + 1/2 O2:H2O (Water) = Molecule, H (Hydrogen) = Element, O (Oxygen) = Element. Thus,
a molecule is a bonding of two or more atoms which may be of the same element or of different
elements.
Compound: A substance that can be broken down into two or more simpler substances. (A compound is
made up of millions of molecules)
Element: The smallest part of a substance that retains the same properties of that substance and cannot
be broken down any further.
Atom: The smallest particle of an element which retains the distinct structure characteristic of an
element. Atoms are building blocks for engineering materials. All substances are made up from atoms; a
substance made from only one type of atom is called an element. The smallest and simplest is the
hydrogen atom and the largest is uranium. Atoms are the building blocks of the universe. Atoms are so
small that millions of them would fit on the head of a pin. Atoms are made of smaller particles. The
center of an atom is called the nucleus. It is made up of two sub atomic particles approximately the
same size called protons (positively charged particles) and neutrons (electrically neutral particles) that
clump together. They weigh 1.67 x 10-24 grams each. Protons and neutrons are very small, but electrons
(9.11 x 10-28g) which are tiny particles found in atoms, are much, much smaller 1,836 times smaller, to
be precise. Reason why almost the entire mass of the atom is concentrated in the nucleus.
The positively charged nucleus is surrounded by a sufficient number of orbiting electrons (negatively
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charged: -1.6 x 10 Coulomb) to keep the atom as a whole neutral, the positive charge of the protons is
equal to the negative charge of the electrons.

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The electrons spin on their own axes as they rotate around


the nucleus in orbits at relatively great distance from the
nucleus (radius of 0.05 2 nm). If the nucleus were the size of
a tennis ball, the atom with its electrons would be several
kilometers.
The more used picture looks like a mini planetary system. But
quantum mechanics tells us that this analogy is not correct
but Electrons move not in circular orbits, but in fuzzy orbits.
If you could see an atom; it might look a little like a tiny center
of balls surrounded by giant clouds (or energy levels).
Electrons are held in their levels by an electrical force. The
protons and electrons of an atom are attracted to each other
as they both carry opposite electrical charge.

Fig.0.1: A carbon atom has 6 protons and six neutrons in the nucleus, two electrons in the inner energy
level, and four electrons in the outer energy level.
When an atom is neutral, it has an equal number of protons and electrons. The neutrons carry no charge
and their number can vary. An element is a substance composed of atoms that have a given number of
protons that determines the elements identity, that is:
Atomic Number: Z = p =e. Every atom of hydrogen, for example, has one proton and one electron. Every
atom of carbon has six protons and six electrons.
Atomic mass also termed as atomic weight or mass number of an element is the combined mass of its
protons, neutrons, and electrons (A = e + n = p + n). E.g A Chlorine= 17+18=35; for Fe the atomic number of
iron is 26 (Z=26) and the atomic mass number is 56 (A = 56). This means that each iron atom has 26
electrons, 26 protons and 30 neutrons
Atoms of the same element may have different numbers of neutrons, but they will all have the same
number of protons atomic number (Z) or electrons. Thus atomic number is a fundamental property of
an atom.
Isotopes: Isotopes of an element have the same atomic number but differ in their atomic mass number
because, even though they have the same number of electrons and protons (electrically neutral), they
differ in the number of neutrons. Example of Ordinary Hydrogen: Hydrogen (H11): 1 electron, 1 proton
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and 0 neutrons whereas H2 Deuterium (H21) has one neutron: 1 electron,1 proton and 1 neutrons and H3
Tritium (H31) has two neutrons: 1 electron,1 proton and 2 neutrons; Chlorine35 has 18 neutrons and
Chlorine 37 has 20neutrons.
To calculate the mass of isotope, we use the following rule M = f1xm1 + f2xm2 + f3xm3 (f: isotope
proportionality content in the mixture and m: 1, 2, 3 corresponding atomic masses)
The atomic mass unit (amu) is often used to express atomic weight. 1amu is defined as 1/12 of the
atomic mass of the most common isotope of carbon atom that has 6 protons (Z=6) and six neutrons
(N=6). Mproton Mneutron = 1.66 x 10-24 g = 1amu. The atomic mass of the 12C atom is 12amu.
The atomic weight of an element = weighted average of the atomic masses of the atoms naturally
occurring isotopes. Atomic weight of carbon is 12.011amu. The atomic weight is often specified in mass
per mole.
A mole is the amount of matter that has a mass in grams equal to the atomic mass in amu of the atoms
(A mole of carbon has a mass of 12 grams). The number of atoms in a mole is called the Avogadros
number, Nav= 6.023 1023.
Nav= 1gram/1amu.
Example: Atomic weight of iron = 55.85amu/atom = 55.85 g/mol
The electrons usually remain within a well-defined region at a relatively constant distance from the
nucleus. These well-defined regions are called energy levels. Within various energy levels, there are
areas of different shapes, called orbitals, where there is a high probability that the electrons will be
found. Actually, we cannot tell how it moves, but only can say what is the probability of finding it at
some distance from the nucleus. Only certain orbits or shells of electron probability densities are
allowed. The energy level closest to the nucleus can hold a maximum of two electrons. The next level
can hold up to eight. The outer levels can hold more.
The electrons in the energy levels closest to the nucleus have a strong force of attraction to the protons,
i.e. they are stable. Sometimes, the electrons in the outermost energy level are not strongly held. Those
electrons are called valence electrons and they can be pushed or pulled from their energy level by a
force. These are the electrons that are typically involved when chemical reactions occur. For that
reason, they are largely responsible for the chemical behavior of the element.
On modern periodic table, Group number indicates the number of electrons available for bonding:
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0: Inert gases (Helium,...krypton, xenon, radon) have filled sub-shells: chemically inactive
IA: Alkali metals (Li, Na, potassium, rubidium, cesium, francium) have one electron in outermost
occupied s-sub shell - eager to give up electron chemically active
- VIIA: Halogens (Fluorine, Bromine, Chlorine, Iodine, Astatine) missing one electron in outermost
occupied p shell - want to gain electron - chemically active.
Electronegativity is a measure of how willing atoms are to accept electrons: Sub-shells with one electron
have low electronegativity; sub-shells with one missing electron have high electronegativity therefore
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electronegativity increases from left to right.

Metals are electropositive since they can give up their few valence electrons to become positively
charged ions.
0.1.2 Bonding energy and bonding forces

The repulsion between atoms, when they are brought close


to each other, is related to the Pauli principle: when the
electronic clouds surrounding the atoms starts to overlap,
the energy of the system increases abruptly.
The origin of the attractive part, dominating at large
distances, depends on the particular type of bonding.
Forces can be calculated from the potential energy of
interatomic interaction. For example, for a system of
two atoms (e.g. a diatomic molecule), the potential
depends only on the distance between the atoms U(r12)

Fig.0.3: Typical potential well for two interacting atoms

The interatomic
distance (rij) is expressed in Angstroms
Fig.0.4: Force and energy variation in terms of interatomic distances
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The electronvolt (eV) is the unit used to describe atomic bonding energy and is defined as energy lost or
gained by an electron when it is taken through a potential difference of one volt.
Mathematically; E = q V where, q=1.6x10-19 Coulombs and V=1volt
Hence, 1eV = 1.6x10-19 J

0.1.3 Electronic configuration


Electrons form a cloud around the nucleus in which they are arranged according to their potential
energy in different principal energy levels or main shells, denoted by number 1,2,3,4,5,6 and 7 or by
letters K,L,M,N,O,P and Q. These main shells contain sub-shells (s, p, d, f) and sub-sub-shells also.
The shells are identified by a principal quantum number n, which can be related to the size of the shell, n
= 1 is the smallest; n = 2, 3... are larger. The second quantum number l, defines sub-shells within each
shell. Two more quantum numbers characterize states within the sub-shells.
Maximum number of electrons in a main shell is 2(n)2. E.g.: For M=2(1)2=2, L: 2(2) 2=8, M=2(3)2=18,
N=2(4)2=32. Beyond N-shell the formula doesnt hold, all the last 3 shells has 32 maximum only.
Maximum number of electrons in a sub-shell or an orbital is 2(2l + 1). E.g.
(1) For s-sub-shell, L=0 its maximum number of electrons is 2. The symbol 2s, 3s, 4s denotes the s-sub
shell of first, second third and fourth energy levels respectively

Fig.: Simple model of atomic structure for several elements : (a) hydrogen , (b) helium, (c) fluorine, (d)
neon, (e) sodium.
(2) For the p-sub-shell, l=1 can have the maximum of 6es. The symbol 2p, 3p, 4p denotes the p-sub
shell of first, second third and fourth energy levels respectively
(3) For d-sub-shell, l=2 thus the maximum is 10. The symbol 3d, 4d, 5d denotes the d-sub shell of third
and fourth energy levels respectively

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(4) For f-sub-shell, l=3 hence the maximum is 14es. The symbol 4f, 5f denotes the f-sub shell of fourth
and fifth energy levels respectively
Exercise: An element with atomic number 50 has all its inner energy levels filled up except 4f level,
which is empty. Determine its expected valence? Soln.: its electronic configuration is : 1s2, 2s2, 2p6, 3s2,
3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p2. The deficiency on 5p-level is 4 es, therefore the valence is -4. All
elements with similar electronic configuration can be placed in the same group, thus the significance of
atomic number lies in the classification of elements in arranging them in the periodic table.
0.1.4 Modern periodic table
The modern periodic table is divided into four blocks:
(a) S-block: elements whose valence electrons lie in s-sub shell (group IA: also named Alkali metals
with one valence electron, and IIA: two valence electrons)

Fig.0.5: Bohrs/ modern periodic table.


(b) P-block: elements whose valence electrons lie in p-sub shell, namely groups IIIA, IVA,VA,VIA,VIIA
and zero. The group number designates the number of valence electron and zero group (noble or
inert gases) has none, i.e. its outermost shell is completely filled with electrons.

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(c) D-block: elements whose valence electrons lie in d-sub shell called transition elements, notably
groups IIIB, IVB,VB,VIB,VIB,IB and IIB. The group VIII consists of 3 sub-groups.
(d) F-block: elements whose valence electrons lie in f-sub shell. Elements with atomic number 58 to 71
are termed Lanthanides and those from 90 to 103 are actinides. These two series of elements
have similar properties they are placed in the bottom of periodic table.
Most substances dealt with in industry and everyday life are categorized as organic or inorganic:
Organic materials are usually derived from living things; they contain the element C (and usually
H) as key part of their structure (e.g.: Petroleum products, plants and animals).
Inorganic materials are those substances not derived from living things (e.g.: Sand, rock, water,
metal and inert gases).
The field of engineering materials deals with both areas: metallurgists and ceramists deal primarily with
inorganic substances; on the other hand; Plastic engineers deal primarily with organic substances. Basic
ingredients used to make both organic and inorganic materials are Elements. Many of these elements
have a little industrial importance.
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Some of the elements are used as engineering materials in their pure elemental state. Metals
like Be, Ti, Cu, Au, Ag, Pt, Pb, Hg and many of refractory metal W, Ta, Mo, Hf are used to make
industrial items.

Many metals are used in pure state for electroplating durable goods, tools and electrical
devices: Cr, Ni, Cd, Sn, Zn, Os, Re, Rh.

In the non metal category:

C is used in industrial applications for motor brushes and wear parts and in the cubic form as
diamond for tools.

The inert gases in elemental form (ions and molecules) are used for industrial applications for
protective atmosphere and the like.

A larger percentage of engineering materials utilize the elements in combined forms; in alloys (a metal
combined with one or more other elements), in compounds (chemically combined elements with
definite proportions of the component elements) and to a smaller degree; in mixtures (a physical blend
of 2 or more substances). These combinations of the elements can be solids, liquids, or gases.

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Element names in blue are liquids at room temperature


Element names in red are gases at room temperature
Element names in black are solids at room temperature

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Engineering materials and metallurgy
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0.1.5 Interatomic bonding in solids


Solids are formed when definite bonds exist between component atoms or molecules. In the liquid state
or gaseous state, atoms or molecules are not bonded to each other. Atoms having electrons valence of
the same charge push each other but those of different charges attract each other.
0.1.5.1 Primary bonding: e- are transferred or shared. They are strong (100-1000 KJ/mol or 1-10
eV/atom)
(a) Covalent bonds: electrons are shared between the molecules i.e. are localized between the
neighboring ions and form directional bond between them; to saturate the valence. The ions repel
each other, but are attracted to the electrons that spend most of the time in between the ions.
Example: H2 (outer shell).

Example: CH4
Carbon has 4 valence electrons, needs 4 more H: has 1 valence electron, needs 1
more. Electronegativities are comparable. Same case applies to long hydrocarbon
chains polyethylene nC2H4 and diamond molecules. Solids with covalent bonding
generally possess high hardness and low electrical conductivity.
Fig.0.7: Covalent bond in Cl2 and CH4 molecules
Formation of covalent bonds: Cooperative sharing of valence electrons; Can be described by orbital
overlap; Covalent bonds are highly directional; Covalent bond model: an atom can covalently bond with
at most 8-N, N = number of valence electrons
Example: Cl2 molecule. ZCl =17 (1S2 2S2 2P6 3S2 3P5). N = 7, 8 - N = 1 can form only one covalent bond
They have a Low melting point, no conductivity and sometimes are not ductile.
(b) Ionic bonds: Strong Coulomb interaction among negative atoms (have an extra electron each) and
positive atoms (lost an electron). Example: Na+Cl-. Large difference in electronegativity required.

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Na

NaCl

Cl

r
+q

EA = (qz) (-qz) /r
- q E = q2z /r2
R

Electron transfer reduces the energy of the system of


atoms i.e. electron transfer is energetically favorable
accompanied by relative size alteration of ions:
Sodium shrinks whereas Chlorine expands.
A strong electrostatic attraction between charged
ions Na+ cation and Cl- anion along with Na+ Na+ and
Cl-- Cl- repulsion result in the NaCl crystal strucrture
which is arranged so that each sodium ion is
surrounded by Cl- ions and each Cl- ion is surrounded
by Na+ ions; as shown below.

Fig.0.8: Schematic representation of the formation of ionic bond between Na and Cl atoms
The atoms of one element give up their outer electron(s), which
in turn attracted to the atoms of some other element to increase
their electron count in the outermost shell to eight. This bond is
naturally provides a very Strong bond between atoms and as a
properties of solid materials with the ionic bonding include low
electrical conductivity and poor ductility.
Attractive coulomb interaction between charges of opposite sign:

Repulsion due to the overlap of electron clouds at close distances


(Pauli principle of QM):
Fig.0.9: Repulsive, attractive and net energies in terms for interatomic distance

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Na has 11 electrons, 1 more than needed for a full outer shell (Neon): 11 Protons Na 1S2 2S2 2P6 3S1
donates e- so 10 e- left to become 11 Protons Na+ 1S2 2S2 2P6
Cl has 17 electrons, 1 less than needed for a full outer shell (Argon): 17 Protons Cl 1S2 2S2 2P6 3S2 3P5
receives e- so 18 e- to turn into 18 Protons Cl- 1S2 2S2 2P6 3S2 3P6
Ionic bonds: very strong, nondirectional bonds
Example: MgO, CaF2, CsCl
Is typical for elements that are situated at the horizontal extremities of the periodic table: Atoms
from the left (metals) are ready to give up their valence electrons to the (non-metallic) atoms from the
right that are happy to get one or a few electrons to acquire stable or noble gas electron
configuration.
Formation of ionic bond:
1. Mutual ionization occurs by electron transfer: Ion = charged atom (Lost or gained electrons); Anion =
negatively charged atom; Cation = positively charged atom
2. Ions are attracted by strong coulombic interaction: Oppositely charged atoms attract each other; An
ionic bond is non-directional (ions may be attracted to one another in any direction)
Ionic bonded materials have:
- High melting point and have poor conductivity; Hard, brittle (most ceramic): any mechanical
force that tries to disturb the electrical balance in an ionic crystal meets strong resistance, in
some special cases, however, significant plastic deformation can be observed, for instance: Nacl
single crystals can be bent by hand in water;
(c) Metallic bonds
It is the atomic bonding mechanism in pure metals and metal alloys. The metallic bonding involves the
sharing of outer shell electrons by all atoms to form a general electron cloud that permeates the entire
block. This bond exists in low valence metals; metal atoms are very small and tend to pack tightly. All
valence electrons in a metal are detached from atoms and combine to form an electron sea that
glues the positive ions together and it moves freely between the atom cores. This type of bonding is
non- directional (bonds form in any direction) thus atoms pack closely. As a result we have a high
ductility/plastic deformation of metals - the bonds do not break when atoms are rearranged
metals can experience a significant degree of plastic deformation.
Examples of metals with typical metallic bonding: Cu, Al, Au, Ag, etc. Transition metals in group VIII (Fe,
Ni, etc.) form mixed bonds that are comprising of metallic bonds and covalent bonds. As a result the
transition metals are more brittle (less ductile) than Au or Cu.

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Fig.0.10: Diagrammatic Representation of the "Metallic Bond".


This cloud provides the attractive forces to hold the atoms together and form a strong, rigid structure in
most cases. Because of the general sharing of electrons and their freedom to move within the metal,
metallic bonding provides typical properties of materials characterized such as good electrical
conductivity , good conduction of heat and good ductility /opaqueness

0.4.2 Secondary bonding: no e- transferred or shared. They are very small forces of attraction acting
between atoms in cases where the formation of ionic or covalent bonds is not possible. Bonding results
from Interaction of atomic/molecular dipoles and it is Weak ( 100 KJ/mol or 0.1 eV/atom)

The secondary bonding is also called van der Waals or physical (as opposite to chemical bonding that
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involves e transfer or sharing). Permanent dipole moments exist in some molecules (called polar
molecules) due to the asymmetrical arrangement of positively and negatively regions (HCl, H2O). Bonds
between adjacent polar molecules permanent dipole bonds are the strongest among secondary bonds.
Polar molecules can induce dipoles in adjacent non-polar molecules and bond is formed due to the
attraction between permanent and induced dipoles.
Even in electrically symmetric molecules/atoms an electric dipole can be created by fluctuations of
electron density distribution. Fluctuating electric field in one atom A is felt by electrons of an adjacent
atom, and induce a dipole momentum in this atom.
This bond due to fluctuating induced dipoles is the weakest
(inert gases, H2, Cl2).
Typical example of Hydrogen bond in water: The H end of the
molecule is positively charged and can bond to the negative side
of another H2O molecule (the O side of the H2O dipole)
Fig.0.12: Hydrogen bond secondary bond formed between two permanent dipoles in adjacent water
molecules.
Basically similar forces also act between atoms which are already bounded in neighboring molecules,
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giving rise to weak Van der Waals forces between long-chain molecules in polymers.
Examples of bonding in Materials:
Metals: Metallic
Ceramics: Ionic and Covalent
Polymers: Covalent and Secondary
Semiconductors: Covalent or Covalent and Ionic
The bonds that hold atoms or molecules together can be very specific and orderly i.e. highly regular
arrangement of atoms: atoms or ions, self-organized in a 3D periodic array (they have a crystal structure
.e.g.: Many metals), or they can be less well defined to mean that they not have a repetitive three
dimensional pattern of atoms: solid with considerable disorder in their structure (They are said to be
amorphous. E.g.: Plastics and glasses). Crystallinity or lack of same is measured by x-ray of electron
diffraction techniques.

Fig.0.13: Amorphous, crystalline and polycrystalline structures


AMORPHOUS
This is a structure with no crystals and often results from rapid cooling. For example molten sugar
poured onto a cold surface forms an amorphous glass like structure instead of crystallizing. The
structure is uniform with the molecules having random positions within it. The mechanical properties
are usually the same in all directions. Liquids are amorphous and when a metal melts, it changes from a
crystalline structure into an amorphous liquid
CRYSTALLINE
Many materials crystallize when cooled slowly e.g. sugar and salt. As solidification occurs the molecules
bond together in regular patterns to form individual crystals or grains that join with other similar crystals
at the boundary. When processed, the crystals may be aligned or elongated in one direction producing
different properties in different directions. In crystalline structure, the atoms are located at regular and
recurring positions in three dimensions. The pattern may be replicated millions of times within a given
crystal. The structure can be viewed in the form of a unit cell, which is the basic geometric grouping of
atoms that is repeated. There are several types of pattern in which metallic atoms can arrange
themselves on solidification, but the most common is as follows :

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Fig.: The three principle types of structural in which metallic elements crystallize: Body-Centered-Cubic,
Face-Centered-Cubic and Hexagonal-Closed-Packed.
The atoms that belong to the unit cell are called the basic atoms, its number is different from one shape
of arrangement to another, and this number can be found from the following equation:
Where N: is the number of the basic atoms in the unit cell; NC: is the number of the atoms in the corner;
NI: is the number of the atoms inside the cube; NF: is the number of the atoms in the center of the face.
When a solid has a crystalline structure, the atoms are arranged in repeating structures called unit
cells i.e. smallest repeating unit of the lattice. The cells form a larger three dimension array called a
lattice i.e. a 3-dimensional system of points that designate the positions of the components (atoms,
ions or molecules) that makes up the substance.

Fig.0.14: Representation of part of a space lattice with a unit cell outlined.


The unit cell is the smallest parallel surfaces of the crystalline structure that can be removed or repeated
in different directions. It is also differ from each other in shape or size in the crystalline lattice from one
material to another.
When a crystalline solid starts to form from molten or gaseous state, these cells will tend to stack in a
three dimensional array, with each cell perfectly aligned, and they will form a crystal. If many crystals
are growing in a melt at the same time, the crystals will eventually meet and form grains. The junctions
of the crystallites are called grain boundaries.
Two closely related features differentiate noncrystalline from crystalline materials:
1. Absence of long range order in the molecular structure of a noncrystalline. It can be visualized with
reference to figure below. They closely packed and repeating pattern of the crystal structure and
random arrangement of atoms in the noncrystalline materials.
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Fig.: Difference in structure between (a) crystalline and (b) noncrystalline materials.
2. Differences in melting and thermal expansion characteristics. It could be demonstrated by a metal
when it is melts. When the metal is molten an increase in volume compared to the materials solid
crystalline state. This effect is characteristic most materials when melted (a noble exception is ice; liquid
water is denser than ice).
0.2 MATERIAL STRUCTURE
0.2.1 CRYSTALLINE STRUCTURE OF SOLIDS

Crystallographers have shown that only seven different types of unit


cells are necessary to create all point lattice; Cubic: a = b = c; = = =
900; Tetragonal: a = b # c; = = = 900; Rhombohedra: a = b = c; =
= # 900; Orthorhombic: a # b # c; = = = 900; Hexagonal: a = b # c;
= = 900 and = 1200 Monoclinic: a # b # c; = = 900 and # 1200;
Triclinic: a # b # c; # , # 900
Fig.0.15: crystal systems illustrative angular and longitudinal gauging
To discuss crystalline structures, it is used to consider atoms as being hard spheres with well-defined
radii. In this hard-sphere model, the shortest distance between two like atoms is one diameter.
0.2.1.1 Atomic packing in crystalline structure
(i) Simple cubic (SC): 1/8 atom at 8 corners=1atom
Vc = a3 = 8r3
a=2r

Va = 4r3/3=4(0.5a)3/3

1/8

18

PF=n x va/vc= 0.52


Interatomic distance (Lattice parameter)
Atom (Nucleus) location

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Fig.0.16: Simple cubic structure atomic packing


(

Fig.: Simple cubic structure as a unit in the crystal structure


Coordination number=6(number of nearest neighbours). Rare due to poor packing (only Polonium has
this structure); close-packed directions are cube edges
(ii) Body-centred cubic (BCC)

Fig.: Body centred cubic structure


Close packed directions are cube diagonals (note: all atoms are identical, the center atom is shared
differently only for ease of viewing). Coordination number is 8, unit cell contains: 1 + (8 x 1/8) = 2
atoms/unit cell. Close-packed directions length = 4R = 3 a. Where D: is the atomic diameter, a : is the
lattice constant, r : is the atomic radius

Fig.: Body centred cubic structure cut through completely bonded atoms.
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(
(
( )

[(

)
)

) ])

Fig.: Determination of atomic packing of BCC


(iii) Face-centred cubic (FCC)

Fig.: Atomic arrangement in the Face centred cubic structure.


Close packed directions length = 4R = 2a
Coordination number is 12, unit cell contains: (6 x 1/2)+ (8 x 1/8) = 4 atoms/unit cell

Fig.: Determination of atomic packing of FCC


{

)
[( )

[( )

( )
20

]
(

(
[(

)
)

) ])

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(iV) Hexagonal Closed Packed (HCP)

Fig.: FCC atoms packing


There are two lattice constant, a and c as shown, that parameter a is
equal to one atomic diameter [a = D] , the parameter c is the high of the
hexagonal structure. From the hexagonal structure basics : c/a =1.633
and r=a/2. So the volume of the basic atom is:
[

( ) ]

And the volume of the unit cell is:

Fig.: Hexagonal structure with unit cell outlined, and showing relationship between a and c.
Example: The atomic radius of an iron atom is 1.238X10-10m. Iron crystallizes as BCC. Calculate the
lattice parameter of the unit cell, a. How many atoms are contained within the BCC unit cell? Also find
the atomic packing factor?
Soln.: For BCC unit cell

; therefore:

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There are 9 atoms: 8 in the corners and 1 in the center of the cubic
[

) ]

Theoretical density of metals = mass/Volume = nm/VA


Where m is atomic mass, n: number of atoms in each cell, V=volume of a unit cell, Avogadros number
(A) = 6.02 x 1023Atoms/g mole
The ranking of density generally follows:
Metals: largest; ceramics: intermediate; polymers: smallest; composites: intermediate

0.2.2 CRYSTAL GEOMETRY


0.2.2.1 Bravais crystal systems
The crystal geometry is based on cubic array dimensions
Unit cell

Lattice
points

Fig.0.21: Lattice parameters used for a unit cell


a, b, c, , , and are called lattice parameters
The crystal system is found in 7 types:
Z
Unit cell

900
900
X
22

Y
1200

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Fig.0.22: Hexagonal crystal geometry


Cubic: a = b = c; = = = 900

Tetragonal: a = b # c; = = = 900

Orthorhombic: a # b # c; = = = 900

Hexagonal: a = b # c; = = 900 and = 1200

Monoclinic: a # b # c; = = 900 and # 1200

Triclinic: a # b # c; # , # 900

Trigonal: a = b = c; = = # 900

Fig.0.23: August Bravais 14 standards unit cells to describe all possible lattice networks by variation of
the basic unit cell for the seven crystal systems
4 types of unit cell: primitive (P), Boy centred (I), Face-centred (F), Side centred (C)

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Fig.0.24: Bravais Lattices

0.2.3 Crystal planes, directions and miller indices


Now that we know how atoms arrange themselves to form crystals, we need a way to identify directions
and planes of atoms.
Why to know them?
- Deformation under loading (slip) occurs on certain crystalline planes and in certain
crystallographic directions. Before we can predict how materials fail, we need to know what
modes of failure are more likely to occur.
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Other properties of materials (electrical conductivity, thermal conductivity, elastic modulus) can
vary in a crystal with orientation (anisotropy).

0.2.3.1 A planes orientation, in every crystal system, is described in terms of coordinates through which
they pass, i.e. in space, it satisfies the equation: x/a + y/b + Z/c = 1, where a, b, c are the intercepts on
the x, y, z axes respectively. The intercepts are measured in terms of a unit length.
Any crystallographic plane can be designed by miller indices (hkl), wherein Miller suggested that it is
more useful to describe the orientation of a plane by the reciprocal of its numerical parameters rather
than by its linear parameters. Therefore, h = 1/a, k=1/b and l=1/c.
E.g. consider a plane ABC with intercepts 1, 2 and 3 along x-x, y-y and z-z respectively
Planes orientation are 1,2,3 or a=1, b=2, c=3
Miller indices (1:1/2:1/3). By multiplying by the
denominators least common multiplier (LCM) 6,
we get alike plane belonging to the same family
of parallel planes abc(6:3:2). The ratio sign (:)
can be omitted to turn into digits (632)
Fig.0.25: Same family parallel planes and miller indices
Involved procedural routine for evaluation of miller indices of a crystal plane is as indicated:
a) Choose three axes parallel to edges of the unit cell and determine the intercepts of the plane with
the axis in terms of a, b and c. ensure that there is no intercept with the origin.
b) Calculate the reciprocals of the intercepts, h = 1/a, k = 1/b, l = 1/c then rationalize and clear all
fractions by multiplying each one of them with their LCM such that h, k, l are integers
c) Enclose the result in brackets (h k l), negative value should be written with a bar on top.

(001)
(010)
b

Z
Not allowed

Y (100)
X

Not allowed
Y
(00 )

Fig.0.26: Miller indices for three faces of the cubic unit cell
The other three faces are represented by shifting the origin of coordinated system to another corner of
unit cell; for example the plane EFGH may be represented by shifting the origin from point H to point
D. Consequently, minus value for a intercepts appear along x-x axis with b/c infinity intersections
along y-y and z-z axes. Similarly remaining two planes are evaluated (0 0) and ( )
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Fig.0.27: Miller indices for three opposite faces of the cubic unit cell
As the six planes of the cubic unit cell are of the same geometry/form; they are represented by the
indices of one of the planes enclosed in curly brackets or braces {}. Hence, {100} will represent a set of
six planes of that unit cubic cell (100), (010), (001), ( 00), (0 0) and ( ). Similarly, {110} represents a
set of six planes (110), (101), (011), ( 0), (10 ) and ( ). These planes also represent diagonal planes.

Plane (110)

Planes ( 10)

Plane (101)

Plane (10 )

Plane (011)

Each diagonal is formed


by joining two opposite
edges of the unit cube
cell that have 12 edges
i.e. 6 diagonal faces
represented by {110}

Plane (01 )

Fig.0.28: 6 diagonal planes of a crystal cubic unit cell


Proceeding alike, {111} represents a set of four triangular planes of the unit cubic cell (11 ), ( ) ( )
and ( )

Fig.0.29: 4 triangular diagonal planes of a crystal cubic unit cell


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Major features of miller indices:

Miller indices define a set of parallel planes as they have same miller indices
Miller indices of two parallel planes may also have the same ratio (e.g. 844 and 422 or 211)
Planes parallel to one of the co-ordinate axes has an intercept of infinity

Exercises
1. Compute the miller indices for the following planes [soln: the plane is parallel to y-y and z-z; (200)]

2. Draw the planes (112), (020), (120), (220), (221) and (211)

0.2.3.2 Crystal directions: A crystallographic direction can be defined as a line joining any two points of
the space lattice, or the line of intersection of two planes. In general, they are represented in terms of
three axes with references to the origin and a lattice point represents the lattice point. The directions
are represented by small set of integers enclosed in square blackest [ ] i.e. [hkl]. The procedure for
determining the directions is as summarized below:
(a) Establish axes system and Determine the coordinates of the beginning and end of the direction
vector AB. A(x1,y1,z1); B(x2y2z2)

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(b) Evaluate the magnitude by subtracting negative coordinates of A from B. h = x2 x1; k=y2 y1; l=z2 z1
B (x2y2z2)

A(x1,y1,z1)

(h1 k1 l1) intersecting (h2 k2 l2), the line of intersection is described as a


direction [hkl] defined by the cross product (h1 k1 l1) X (h2 k2 l2)
E.g.: P (1, 1, 0) and Q (0, 1, 1) the resulting direction is [T01]; R (1/2, 0, 1)
and O (0, 0, 0) the resulting direction is [-1/2 0 -1] or [102]
A unit cell of a cubic crystal, in which the point O represents the
origin and A,B and C represent the lattice points along x-x, y-y and z-z
axes respectively. The line joining O and A (i.e. OA) represents the
crystal direction of the lattice point A. similarly, OB and OC represent
the crystal directions of the lattice point B and C respectively.
Procedures adopted to find Miller indices of a spatial direction are
detailed below:

Fig.0.32: Crystal directions

(i) Draw a straight line OD passing through the origin O and parallel to
the crystal direction RS, whose Miller indices are required to be
determined.

(ii) Take any point P on the line OD and draw perpendiculars PL, PM and PN on x-x and y-y axes
respectively
(iii) Find the intercepts of OL, OM and ON in terms of axial units
(iV) Reduce these intercepts in the smallest integers. This is done by dividing the values of three
intercepts with the least value of the three intercepts.
(V) Enclose the smallest integers in square brackets which represents the Miller indices of the line RS
[100], [010] and [001] represent directions along x-x, y-y and z-z axes respectively. The other 3 directions
are found by shifting origin to another corner; e.g. DH direction represented by swapping the origin at D,
HG at G and HE at E; the values of intersects become minus.

Fig.0.33: Directions along three axes of a coordinated crystal system

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As all the crystal directions, in a cubic unit cell are of the same form, the Miller indices of such crystal
directions are represented by the indices of one of the crystal directions enclosed in a carat < >. Hence
<100> represents a set of six directions [100], [010], [001], [ 00] [0 0] and [00 ].
It is noticeable from 4 shown figures, every crystal direction is
perpendicular to the plane that they have same Miller indices: HD/[100]
with ABCD, HG/[010] with BFGC and HE/[001] with AEFB. As a conclusion;
in a cubic system, all the directions and planes with identical indices are
perpendicular.
For this leftward figure, HA [101], HC[110], HF[011] and HB[111]. Crystal
directions having negative values along x, y and z axis are likewise
represented
Fig.0.34: Some important crystal direction in a cubic unit cell

Fig.0.35: Example of directions


EXERCISES
Sketching directions when Miller indices given: Sketch the plane with the given miller indices. Then;
through the origin, draw a line normal to the sketched plane, which will give the required direction.
1. Draw the following planes and directions in F.C.C structure with the following Miller indices (112),
(001), (101), (321), (201), (111), (010), (111), (011) and (001)?
Soln.: First sketch a plane with intercepts reciprocals of miller indices (112), that is 1,1 and 0.5. then
through the origin, draw the required direction (a line normal to the sketched plane). Proceed alike for
other planes and directions

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2. Calculate the atoms per unit cell of metallic Zinc. Draw (121) plane and <121> direction in a cubic
lattice.
Soln.: we know that Zinc has FCC structure. The total number of atoms per unit cell may be obtained as
follows: the FCC structure has 8 corners and 6 faces. It has an atom at each corner and another at the
centre of each face. The corner atom is shared by 8 cubes, and each atom at the face centre is shared by
2 cubes. The number of atoms in all six faces = 1/2 x 6 = 3, and number of atoms in all the corners = 1/8
x 8 = 1. Hence the total number of atoms = 3+1 = 4atoms.
Let h,k and l = intercepts along x-, y- and z- axis. We know that Miller
indices of given plane 1:2:1 =

or

Thus, the intercept along x-axis is one unit, one-half along y-axis and
one unit along z-axis. Knowing this, the (121) plane and its
perpendicular line (direction <121>) can be sketched as shown.
Noteworthy postulates to recall about Miller indices
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.
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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.

0.2.3.2 Combinatory relationships among planes and directions


1. Inter-planar distance between family of planes {
{

} is given by

Where a is the lattice parameter


E.g. Determine the distance between adjacent {121} planes of copper, which have a lattice parameter of
3.615A.

ao
h l k
2

3.615

1 2 1
2

3.615
1.8 A0
4

2. [

]direction is parallel to the plane (

) if

3. [

]direction is normal to the plane (

) if
) and (

4. The direction of intersection between two planes(


product:
(
(

The intersectional direction line is will then be [

) is found through their cross


)

5. To find out the angle between the two intersecting planes, we use the dot product:
| || |
| || |

E.g. Calculate the angle, and the line of intersection between the two planes (124) and (012)?
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Soln.: Line of intersection found by the cross product [hkl} = (

) (
)
(

then [hkl] = [121]


The angle found by the dot product
| || |

6. Two planes (
7. Two directions [

) and (
] and [

) are normal if
] are normal if

0.2.4 IMPERFECTION IN CRYSTALS


Real crystals are never perfect: they always contain a considerable density of defects and imperfections
which on macroscopic level , in addition to bonding and structure, affect their physical, chemical,
mechanical and electronic properties. E.g.:
- The presence of surface defects such as cracks causes brittle materials like glass to break at small
applied stresses.
It should be noted that defects do not necessarily have adverse effects on the properties of materials.
For instance,
- The existence of dislocations (line defects) in crystals provides a mechanism by which permanent
change of shape or mechanical deformation can occur. A crystalline solid free of dislocations is
brittle and practically useless as an engineering material. While the existence of dislocations in
crystals insures ductility (ability to deform), the theoretical strength of crystalline solids is drastically
reduced by their presence.
- The ability of a ferromagnetic material (such as iron, nickel or iron oxide) to be magnetized and
demagnetized depends in large part on the presence of 2D-dimensional imperfections known as
Bloch walls. These interfaces are boundaries between two regions of the crystal which have a
different magnetic state. As magnetization occurs, these defects migrate and by their motion
provide the material with a net magnetic moment. Without the existence of Bloch walls all
ferromagnetic materials would be permanent magnets. In fact, electromagnets would not exist if it
were not for this type of defect.
- The electrical behavior of semiconductors is largely controlled by crystal imperfections. The
conductivity of silicon can thus be altered in type (n or p) and by over eight orders of magnitude
through the addition of minute amounts of electrically active dopant elements. In this case, each
atom of dopant, substitutionally incorporated, represents a point defect in the silicon lattice. The
fact that such small amounts of impurity atoms can significantly alter the electrical properties of
semiconductors is responsible for the development of the transistor and has opened up the entire
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field of solid state device technology.


All defects and imperfections can be conveniently considered under four main divisions depending on
their dimension:
- 0D, Point defects: atoms missing or in irregular places in the lattice (vacancies, interstitials,
impurities)
- 1D, Linear defects or dislocations,: groups of atoms in irregular positions (e.g. screw and edge
dislocations)
- 2D, Planar defects or interfacial or grain boundary
- defects: the interfaces between homogeneous regions of the material (grain boundaries,
external surfaces)
- 3D, Volume (spatial) defects
We can also add here macroscopic or bulk defects such as pores, cracks and foreign inclusions that are
introduced during production and processing of the solid state.
Point defects are inherent to the equilibrium state and thus determined by temperature, pressure and
composition of a given system. The presence and concentration of other defects, however, depend on
the way the solid was originally formed and subsequently processed.
0.2.4.1 Point imperfections
Formation of point defects
An incontrovertible law of nature states: Nothing is perfect. This law applies to humans as well as to
the inorganic world of crystalline solids and can be formulated as the 2nd law of thermodynamics:

where F is the free energy of a given system, H is the heat content or enthalpy and TS is the entropy, or
disorder, term. If a reaction takes place at a temperature T, we find the change in F (DF) related to a
change in H (DH), the heat content, and possibly also a change in TS (TDS).
Such is the case when defects are formed in a perfect solid: The energy distribution in a solid (MaxwellBoltzmann) suggests that a number of individual atoms may acquire enough thermal energy to be
displaced from the equilibrium lattice site into an interstitial position. Hence; Under temperature
activated processes, some atoms may leave their normal positions to occupy interstitial positions. This
process results simultaneously in the formation of a vacancy and an interstitial atom. The number of
vacancies (defects) at equilibrium Nd at a certain temperature T is given by:
(
);
Where N is the total number of atomic sites per cubic meter or per mole. Ed or H is the activation
energy necessary to form a defect. A is the proportionality constant, T is the absolute temperature (in
Kelvin) and k the Boltzmanns constant, (k=1.380 X 10 -23 JK-1)
This process of point defect formation requiring energy and leads to lattice strain which constitutes, as
discussed earlier, an increase in the heat content of the system (DH is positive and increases linearly
with the number of defects formed). The departure from perfection by the generation of defects leads
to disorder (DS is positive). The magnitude of disorder generated (DS) is very large during the initial step
from perfection to slight disarray, but the increase in disorder (with a given number of defects
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generated) decreases as the overall disorder increases.


Correspondingly the term TDS drops rapidly at the
beginning and then flattens out. The net result, free
energy, exhibits a minimum for a certain number of
defects in the solid [equilibrium defect density = f
(temperature)]; the Fminimum suggests also that the
transition from perfection to equilibrium defect structure
is spontaneous: it occurs naturally!
The associated equilibrium energetics is clear: Calculations
of the thermal energy of atoms in a lattice show that the
average vibrational energy of lattice atoms is much less
than 1 eV
Fig.: Thermodynamics of point defect formation
(the approximate energy change associated with vacancy formation, i.e., the least amount
of energy required to form a vacancy) at room temperature. Therefore a lattice atom will only acquire
the energy Hd, the energy required to form the defect, upon the occurrence of a large energy
fluctuation. Since the relative probability of an atom having energy Hd or more in excess of the ground

state energy is
the probability that an atomic site is vacant varies in the same way. In a (molar)
crystal containing N atomic sites, the number nd of vacant sites is as already shown in equation.
Vacancies and interstitial atoms may be also triggered by Irradiation with x-rays; An imperfect packing
during crystallization; Plastic deformation; Quenching and Heating.

Point Defects in Pure Metallic Systems: They are defects of atomic dimensions. A much localized
interruption in the regularity of a lattice due to either: The absence of a matrix atom (vacancy), the
absence of a matrix atom and/or the presence of a matrix atom in the wrong place. The simplest point
defects are as follows:
Vacancy is an atom site, normally occupied in the perfect crystal, from which an atom is missing at a
certain crystal lattice position. Often the term vacancy is used to denote a so-called Schottky
defect, which is formed when an atom or an ion leaves a normal lattice site and repositions itself in
a lattice site on the surface of the crystal. This may be the result of atomic rearrangement in an
existing crystal at a high temperature when atomic mobility is high because of increased thermal
vibrations. A vacancy may also originate in the process of crystallization as a result of local
disturbances during the growth of new atomic planes on the crystal surface. Vacancies are point
defects of a size nearly equal to the size of the original (occupied) site; the energy of the formation
of a vacancy is relatively low - usually less than 1 eV.
Self-interstitial atom extra atom in an interstitial position;
Interstitial impurity atom extra impurity atom in an interstitial position between matrix atoms.
Substitution impurity atom impurity atom, substituting an atom in crystal lattice.
Whether a foreign atom will occupy a substitutional or interstitial site depends largely on the size of
the atom relative to the size of the site. Small atoms are usually interstitial impurities, while larger
atoms are usually substitutional impurities.

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Fig.0.38: Point defects in crystals


The concentration of vacant lattice sites in pure materials is very small at low temperatures - about one
vacancy every 108 atom sites - and increases with increasing temperature to about one vacancy every
103 sites at the melting temperature. Vacancies are important because they control the rate of matrix
(or substitutional) atom diffusion - i.e., atoms are able to move around in a crystalline solid primarily
because of the presence of vacancies. (The mechanism by which they move is the same as that
associated with moving a car in a filled parking lot to the exit).

Fig.: Dynamics of vacancy movements in a close packed solid


Self-interstitials are generally not encountered in close-packed metallic systems, but may be introduced
by irradiation. For example, high-energy neutrons from atomic fission can knock metal atoms from their
regular sites into interstitial sites, creating vacancy-interstitial pairs.
Point Defects in Ionic Solids: Point defects in ionic structures differ from those found in pure elements
because of the charge neutrality requirement. For example, in a pure monovalent ionic material a cation
vacancy must have associated with it either a cation interstitial or an anion vacancy to maintain charge
neutrality. Similar requirements hold for anion vacancies.

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A vacancy pair defect (migration of a cation and


an anion to the surface) is usually called a
Schottky imperfection, and a vacancy-interstitial
pair defect is referred to as a Frenkel
imperfection (an anion or cation has left its
lattice position, which becomes a vacancy, and
has moved to an interstitial position). Selfinterstitials are much more common in ionic
structures than in pure elements because many
ionic compounds have relatively large interstitial
sites available.
Fig.: Point defects in ionic solids.
That is, there are often interstitial sites in the unit cell that have nearly the same surroundings as normal
atom sites. (For example, in BeO the Be atoms fill only one-half the available tetrahedral sites, leaving
four possible cation interstitial sites per unit cell. Thus a Be atom could go from a regular lattice site to
an almost equivalent interstitial site with little distortion of the lattice.)
Foreign atoms in ionic crystals produce defects that also must maintain charge neutrality. For example,
in NaCl a monovalent cation, such as lithium, may simply replace one of the sodium ions as a
substitutional impurity. But a divalent cation, such as calcium, replacing a sodium ion must be
accompanied by either a cation vacancy or an anion interstitial if charge neutrality is to be maintained.
Correspondingly, monovalent impurity cations in a divalent structure (e.g., Na in MgO) must be
accompanied by an appropriate number of cation interstitials or anion vacancies.
In both Frenkel and Schottky defects, the pair of point defects stays near each other because of strong
coulombic attraction of their opposite charges
0.2.4.2 Line imperfections
Line imperfections are called dislocations. A dislocation is a crystal imperfection characterized by regions
of severe atomic misfit where atoms are not properly surrounded by neighbour atoms. When the
dislocation reaches an outside surface of the crystal, it can cause a slip step. There are 2 general types of
dislocations: Edge dislocations and Screw dislocation:
Edge dislocation
It is an extra half plane of atoms inserted into the crystal lattice. Due to the edge dislocations metals
possess high plasticity characteristics: ductility and malleability.

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Fig.: Schematic presentation of a dislocation; the last row of atoms (dark) in the inserted fractional
plane
Line imperfections, or dislocations, in crystalline solids are defects that produce lattice distortions
centered about a line. A dislocation is simply the edge of an extra inserted fractional plane of atoms.
Normally the symbol is used to represent a positive and dislocation (extra fractional plane) and is
used to represent a negative dislocation (missing fractional plane).
The dislocation causes a displacement characterized by the burgers vector; b. the burgers vector is
perpendicular to the edge dislocation.
The plane in which a dislocation moves through the lattice is called a slip plane. With an applied shear
stress the dislocation moves, atomic row by atomic row, and one part of the crystal is displaced relative
to the other. When the dislocation has passed through the crystal, the portion of the crystal above the
slip plane has shifted one atomic distance relative to the portion below the slip plane. In other words,
the motion of the dislocation has caused the crystal to change its shape - to be permanently deformed

Fig.: Plastic deformation of crystalline solid by slip associated with stress induced motion of
dislocation
Plastic Deformation By Slip: When single crystals of metal (or semiconductor) are pulled in tension, they
will begin to deform (elongate) plastically at relatively low stress levels, and blocks of the crystals slide
over one another because of dislocation motion. Simultaneously, so-called slip lines appear on their
surface. It is found that deformation by slip occurs most easily on planes with high atomic density and
with large interplanar spacing, while the direction of slip is in all instances an atomically close-packed
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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


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direction. For FCC structures we therefore observe as the primary slip system {111} planes in <110>
direction, while in BCC structures the primary slip occurs on {110} planes in <111> directions. (It should
be noted that an alternate deformation mechanism is deformation twinning, presently not to be
considered.)
Dislocation Climb: Climb is the name given to the motion of dislocations when the extra half plane is
extended farther into a crystal or partially withdrawn from it.
Clearly, the climb process is not a
motion of the plane, but rather its
growth or shrinking as a result of
the addition of atoms or
vacancies respectively from the
environment of the dislocation

Figure 7 Dislocation climb by (a) loss of atoms to surrounding vacancies and (b) incorporation of
interstitial atoms.
Where dislocations come from?
Dislocations can be created by crystal mismatch in solidification. They can be introduced by External
stresses such as plastic deformation; they can occur by phase transformations that cause atomic
mismatch effects of adding alloy elements. The importance of dislocations to the metal user is that
dislocation interactions within a metal are a primary means by which metals are strengthened. When
metals deform by dislocation motion, the more barriers the dislocations meet, the stronger the metal.
Dislocations are seen and studied only with microscopic and etching techniques since they are atomic in
size.
a) Screw dislocation
It forms when one part of crystal lattice is shifted (through shear) relative to the other crystal part. It is
called screw as atomic planes form a spiral surface around the dislocation line. Slip plane (There is a slip
step produced when a dislocation reaches a free surface)

b
Slip plane

Fig.0.40: Schematic representation of a screw dislocation with a burgers circuit


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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


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0.2.4.3 Planar or interfacial imperfections


Are defects on the external surface of the crystal. Their several different types in solids can be grouped
into the following categories:
(a) Interfaces between solids and gases, which are called free surfaces;
(b) Interfaces between regions where there is a change in the electronic structure, but no change in the
periodicity of atom arrangement, known as domain boundaries;
(c) Interfaces between two crystals or grains of the same phase where there is an orientation difference
in the atom arrangement across the interface; these interfaces are called grain boundaries;
(d) Interfaces between different phases, called phase boundaries, where there is generally a change of
chemical composition and atom arrangement across the interface.
Grain boundaries are peculiar to crystalline solids, while free surfaces, domain boundaries and phase
boundaries are found in both crystalline and amorphous solids.
A. Free Surfaces
Because of their finite size, all solid materials have free surfaces. The arrangement of atoms at a free
surface differs slightly from the interior structure because the surface atoms do not have neighboring
atoms on one side. Usually the atoms near the surface have the same crystal structure but a slightly
larger lattice parameter than the interior atoms.
Perhaps the most important aspect of free surfaces is the surface energy (g) associated with surfaces of
any solid. The source of this surface energy may be seen by considering the surroundings of atoms on
the surface and in the interior of a solid. To bring an atom from the interior to the surface, we must
either break or distort some bonds - thereby increasing the energy. The surface energy is defined as the
increase in energy per unit area of new surface formed. Typical values of surface energies of solids range
from about 101 to 1 J/m2. Generally; the stronger the bonding in the crystal the higher the surface
energy. Surface energies can be reduced by the adsorption of foreign atoms or molecules from the
surrounding atmosphere.
B. Grain Boundaries
In polycrystalline materials, each separate crystal is called a grain. The areas of mismatch between
adjacent crystals are called grain boundaries.
Grain boundaries separate regions of different crystallographic orientation. The simplest form of a grain
boundary is an interface composed of a parallel array of edge dislocations tilt boundary named so
because the misorientation is in the form of a simple tilt about an axis, parallel to the dislocations. Tilt
boundaries are referred to as low-angle boundaries because the angle of misorientation is generally less
than 100. When a grain boundary has a misorientation greater than 10 or 15, it is no longer practical to
think of the boundary as being made up of dislocations because the spacing of the dislocations would be
so small that they would lose their individual identity.
Solids with grain boundaries are referred to as polycrystalline, since the structure is composed of many
crystals - each with a different crystallographic orientation. In the case of iron the grain boundary
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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy

structure can be revealed by preferential chemical attack (etching, the grain boundaries dissolve more
rapidly, leaving a line marking their location.) at the grain boundaries, while the grain structure in
polyethylene is revealed by the use of polarized light.
The anisotropic properties of a crystal grain are discontinuous across a boundary. The atoms along the
grain boundary are more reactive because they possess more energy than interior atoms (lower packing
factor). The microstructure is characterized by grain size, grain shape and grain orientation. The grain
structure is usually specified by giving average grain diameter or by using a scheme developed by the
American Society for Testing and Materials (ASTM: American Society for Testing Materials)
Grain
Grain

Grain boundary

Grain

Fig.0.41: The atomic arrangement in crystals depicting the grain boundary and fine with Coarse grains
The grain size affects the area and length of the grain boundary. It also affects the strength of the
material. A fine grained structure has higher yield strength than coarse grained structure. According to
the Hall-Petch equation, y 0

ky
d

where, 0 is the stress required to move a dislocation, ky is a

constant related to the stress required to create new dislocations and d is the average grain diameter.
The ASTM grain size N can be calculated from the equation N = 2 n + 3. Where n is the number of grain in
one square meter taken at a magnification of 100X. E.g.: how many grains in 1m2 at 100X for n = 3. N =
26 = 64
In polycrystalline samples the individual grains usually have a random crystallographic orientation with
respect to one another, and the grain structure is referred to as randomly oriented. In some instances,
however, the grains all have the same orientation to within a few degrees. In this instance the material
is said to have a preferred orientation or texture.
C. Phase Boundaries
A phase is defined as a homogeneous, physically distinct and mechanically separable portion of the
material with a given chemical composition and structure. Phases may be substitutional or interstitial
solid solutions, ordered alloys or compounds, amorphous substances or even pure elements; a
crystalline phase in the solid state may be either polycrystalline or exist as a single crystal.
Solids composed of more than one element may - and often do - consist of a number of phases. For
example, a dentists drill: a mixture of small single crystals of tungsten carbide (discontinuous) for good
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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy

abrasive characteristics surrounded by a matrix of cobalt (a continuous phase) for and good toughness
and impact resistance. Such polyphase materials are generally referred to as composite materials to
yields a structure with the desired properties.
The nature of the interface separating various phases is very much like a grain boundary. Boundaries
between two phases of different chemical composition and different crystal structure are similar to
grain boundaries, while boundaries between different phases with similar crystal structures and
crystallographic orientations may be analogous to low-angle grain boundaries in both energy and
structure.
The concept of a solid consisting of a continuous phase and a discontinuous phase (or phases) leads to a
simple classification of the various types of composite materials based on the structure (whether
amorphous or crystalline) of the continuous and discontinuous phases.
Continuous Phase
Crystalline

Discontinuous Phase/phases
Crystalline

Crystalline
Amorphous

Amorphous
Crystalline

Amorphous

Amorphous

Examples
All metallic systems such as cast iron, steel, soft solder, etc.;
most natural rocks such as granite and marble.
None of practical significance.
Most man-made ceramics such as building bricks and
electrical insulator porcelain, concrete, partially crystalline
polymers, some polymer-crystalline particle composites.
Fiberglass, asphalt, wood, hydrated cement, other gels.

(a) Vacanciesmissing atoms:


Little impact on strength
(b) Foreign (solute) atom on
interstitial
and
substitutional
sites:
Alloying and heat treating
(c) Line
Defect
=
A
dislocationan extra halfplane of atoms: Greatest
impact on strength and
ductility!!
(d) Grain boundaries: Coarse
GB = weak, Fine GB =
strong and ductile

Fig.: Defects in crystals and related propertiesimpacts


0.2.4.4 Spatial imperfections: Spatial imperfections in crystal include precipitates, pores and bubbles.
Radiation damage often involves the formation of bubbles. The opaqueness of many sintered ceramics
is due to porosity. In this category of imperfections, are included: Gas bubbles in solids porosity, Slag
or non metallic inclusions and Cracks.
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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy

I. ENGINEERING MATERIALS PROPERTIES AND SELECTION


1.1 ENGINEERING MATERIALS PROPERTIES
Each material has a property profile. The properties of engineering materials can be classified into the
following groups: Physical and chemical. The physical properties can also be further grouped into
categories: mechanical, thermal, electrical, magnetic, optical etc. the chemical properties include:
environmental and chemical stability.
Some general properties cannot be classified within these groups:
Density: Mass per unit volume for a material. Relative density of a material is that one compared to
the density of pure water at 40C.

Density ( )

mass(m)
density of themateria l
, Re lative(d )
or the mass of a
volume(V )
density .of . pure.water .at.4 0 C

substance over the mass of an equal volume of pure water


Metals: largest; ceramics: intermediate; polymers: smallest; composites: intermediate
Anisotropy: the characteristic of exhibiting different values of a property in different directions. E.g.
Rubber reinforced with horizontally placed fibers has a high ultimate tensile strength if pulled
parallel to the fibers i.e. horizontally, but a relatively low one if pulled vertically.
Aesthetic properties: It is included the appearance, colour, shape, size, texture and feel, etc

Economic properties: Price/cost(/kg) and availability.


1.1.1. PHYSICAL PROPERTIES
1.1.1.1 MECHANICAL PROPERTIES OF MATERIALS
1. Strength: Materials ability to resist the action of external loads without fracturing. Its measure is
ultimate stress. It falls when heat is applied.
Tensile strength: the ability of a material to withstand tensile (stretching) loads without breaking. i.e.
the ability of metal to return to its original size and shape after being stretched or pulled out of
shape

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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


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As the force of gravity acting on the


load is trying to stretch the rod, the
rod is said to be in tension. Therefore,
the material from which the rod is
made needs to have sufficient tensile
strength to resist the pull of the load.
Fig.1.1: A heavy rod held up by a rod fastened to beam
Compressive strength: the ability of a material to withstand compressive (squeezing) loads without
being crushed or broken. In other words ability of a metal to withstand pressures acting on a given
plane

Fig.1.2: Humans/a component being squashed by the load.


Shear strength: the ability of a material to withstand offset loads, or transverse cutting (shearing
action). Bse the loads are not exactly inline, they are said to be offset.

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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


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Fig.1.3: Chisels shear blades with Rivet joining 2 metal bars together
Fatigue strength (endurance limit) or sometimes referred to as the fatigue limit, it is the maximum
stress amplitude in fatigue below which a material can endure an essentially infinite number of
stress cycles and not endure failure. Generally infinite life means more than 107 cycles to failure

Fig.1.4: stress fluctuation as a function of time


Modulus of rupture: when the material is difficult to grip (as is a ceramic), its strength can be
measured in bending. The modulus of rupture (MOR) is the maximum surface stress in a bent beam
at the instant of failure. One might expect this to be exactly the same as the strength measures in
tension, but it is always larger (by a factor of about 1.3) because the volume subjected to this
maximum stress is small, and the probability to large flaw lying in the highly stressed region is also
small. The MOR strictly only applies to brittle materials. For ductile materials, the MOR is the
ultimate tensile strength.
2. Elasticity: the ability of a material to deform under load and return to its original size and shape when
the load is removed. If it is made from an elastic material it will be the same length before and after the
load is applied, despite the fact that it will be longer whilst the load is being applied. All materials
possess elasticity to some degree and each has its own elastic limits

Fig.1.5: A tensile test specimen with the same length before and after the application of the load
a: Stress (The internal resistance induced in the body when it is subjected to external forces). Types of
stresses: Tensile, compressive, bending and shear stress.
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b: Strain (Initial deformation when a metal is stressed)

Uniform (necking) strain: it is the value of strain at which the area of the specimen begins having
different values at different points, i.e. necking starts
Elastic/youngs modulus, E is the slope of the initial, linear-elastic part of the stress-strain curve in
tension or compression. It is a measure of the rigidity of the material. It is the proportionality
constant of solids between elastic stress and elastic strain and it describes the inherent (natural)
stiffness of a material.
E=Elastic stress/Elastic strain.
For isotropic materials it is related to bulk modulus K and to shear modulus G:
(
)
(
)
, and hence E=K, and
Where is the Poissons ratio; commonly
( )

Fig.1.6: Stress vs strain curve


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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


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Yield strength: The stress at which a material exhibits a specified deviation fro proportionality of
the stress and strain (flow stress). An offset of 0.2% is used for many metals.
Upper yield point
Yield point
Lower yield point
Fig. 1.7: Yield strengths two possible statuses
Only certain metals have a yield point (metals with BCC crystal structure such as iron). If there is a
decrease in stress after yielding, a distinction may be made between upper and lower yield points.
Shear modulus is the initial, linear elastic slope of the stress-strain curve in shear. Also referred to
as modulus of rigidity or torsion modulus, its is the ratio of shear stress divided by the shear strain
in elastic region. G= Elastic shear stress/Elastic shear strain.
For isotropic materials it is related to youngs modulus E and to bulk modulus K and Poissons ratio:
(
)
(
)
(
)
,
When
( ) and
( )
Bulk Modulus, K, measures the elastic response to hydrostatic pressure. Ratio of mean normal
stress to the change in volume

. For isotropic solids, it is related to E and G:


(

(
(

)
)

, E= K, and
When
( )
Poissons ratio, , (dimensionless): it is the negative ratio of the thickness decrease divided by the
length increase as a result of a tensile stress applied to a material. Its value for many solids is close
to 1/3. For elastomers it is just under 0.5
Stiffness (rigidity): The resistance of a material to elastic deformation. It is measured as the area under
the elastic part of stress-strain curve. The rigidity can be also defined as a measure of a materials ability
not to deflect under an applied load. For example, although steel is very much stronger the cast iron the
latter material is preferred for machine beds and frames because it is more rigid and less likely to deflect
with consequent loss of alignment and accuracy. E.g.(see fig.): For a given load the cast iron bar deflects
less than steel bar. However, by increasing the load the Cast iron beam bar breaks, whilst steel bar
merely deflects a little further without breaking. Thus rigid material is not necessarily strong. Rigid
materials are often ductile.

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(a) The tested materials deflect


under a light load in (b) The
tested materials deflect under
heavy load

Fig.1.8: Stiffness (rigidity)


3. Plasticity: property opposite to elasticity. The material is loaded beyond its elastic limit so as to cause
the permanent deformation. Ductility and malleability are particular cases of plasticity.

Fig.1.9: a piece of mild steel strip bent at right angles which does not spring back straight again
Ductility: this term is used when a useful amount of plastic deformation occurs as a result of a
tensile load (Ability of a material to be drawn into wire). . The tensile ductility is the permanent
increase in length of a tensile specimen before fracture, expressed as a fraction of the original
gauge length, i.e it is the ability of a material to undergo large plastic deformation without failure,
also it can be expressed as reduction of area of the specimen during the tensile test.

Fig.1.10: Wire drawing process and comparative graphs between strength, ductility and toughness
stress

High strength, low ductility, low toughness

High strength, high ductility, high toughness

Low strength, high ductility, low toughness


Strain

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Fig.1.11: rivet heading process.

Malleability: this term is used when plastic


deformation occurs as a result of a compressive
load. It allows a useful amount of plastic
deformation to occur under compressive
loading before fracture occurs. In other words,
it is the ability of a material to be rolled or
hammered into thin sheets) or pressed into
various shapes without rupture or fracture.
Such a material is requires for manipulation by
such process as forging, rolling, hammering or
pressing, rivet heading. The most malleable
material is gold; it can be hammered into thin
foils only 0.0025millimetres thick. Other
malleable metals under decreasing order: Ag,
Pb, cu, Al, Sn, Pt, Zn, Fe and Ni. Metals that are
malleable are also ductile.

Superplasticity: a feature of materials to withstand plastic deformation over their limits at high
temperature (usually half of the melting temperature). This effect is caused by dynamic
recrystallization during deformation of the metal
Bauschinger effect: the process where the plastic deformation in one direction causes a reduction
in the yield strength when stress is applied in opposite direction

4. Brittleness: opposite property to ductility and malleability. The material shows little or no plastic
deformation before fracture when a force is applied.
Refer to Fig.: A steel rod can be bent but a grey cast iron rod snaps when you try to bend it.
Temper brittleness: A feature of some materials, which causes the material to become more brittle
after tempering. It can be obtained from the notch-impact test.
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5. Hardness: ability of a material to withstand scratching, surface abrasion and indentation (local plastic
deformation) by another hard body. Often measured by pressing a pointed diamond or hardened steel
ball into the surface of the metal. It is generally defined as the indentor force divided by the projected
area of the indent measuring techniques: Brinell, Vickers, Rockwell, Shore etcIt is an indication of wear
resistance of a material.
Load
indentor

Specimen surface
Fig.1.13: Indentor with load in soft material penetration
Hardness is good indicator for controlling or comparison purposes, but has little meaning for scientific
purposes or calculations
Hardened steel ball only makes a small
indentation in the hard material but it
makes a very much deeper impression in
the softer material.
Fig.1.14: hardened steel ball being pressed first into hard, then soft material by the same load.
Strain hardening exponent: an increase in hardness and strength caused by plastic deformation at
temperatures below the recrystallization range. The measure is the exponent n in the equation
n
n
1=k 1 or ln=lnk + nln 1
Strain rate sensitivity: it is the measure for how fast strain hardening occurs when a material is
deformed plastically. It is defined as
(
)
[
]
(
)
Archard wear constant, kA(m/MN): the volume of material lost from one surface, per unit distance
slid is called the wear rate. The materials ability to resist wear is given by the Archard wear
constant, KA.
; where A is the area of the surface, p is the pressure.

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Volume, V
P3

P
P2
P1
W=V/S

V
S

Area

6. Toughness (Impact strength): the ability of a material to withstand shatter i.e. absorbing energy
without rupturing (e.g.: rubber and most plastics). If a material shatters it is brittle (e.g.: glass).
Also defined as materials opposition to bending or
shearing without fracture. E.g. if a rod is made of
high-carbon steel then it will bend without breaking
under impact of the hammer, while if a glass rod, it
will break by impact loading as illustrated leftwards.
Usually, it is measured by the energy absorbed in a
notch impact test, but the area under the tensile
stress-strain curve is also a measure
Fig.1.16: A metal rod in a vice being broken by impact loading

Fig.1.17: Toughness measure and notch impact test


Fracture toughness:
The fracture toughness KC, is a measure of the resistance of a material to the propagation of a crack.

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It can be measured by loading a sample containing a deliberately introduced crack


on length a=2c and then recording the tensile stress at which the crack propagates.

Where Y is a geometric factor near unity; Measured in this way, Kc has well defined
values for brittle materials (ceramics, glasses, many polymers and low toughness
metals like cast ron). In ductile materials, a plastic zone develops at the crack tip,
which introduces new features into the way cracks propagates. This necessitates
more complex characterization. Nevertheless, for Kc are cited and are useful as a
way of ranking materials.

Fig.1.18: Crack initiation in the material.


7. Resilience: Property to absorb energy and resist shock under impact loads. It is measured by the
maximum amount of energy absorbed per unit volume which can be stored elastically; this energy is
released upon loading. This value can be calculated as the area under elastic part of the stress-strain
curve. This is used particularly for springs.
Damping capacity loss coefficient () dimensionless: the loss coefficient measures the degree to
which a material dissipates vibrational energy
F/A0

F
U

A0

U
L/L

If a material is loaded elastically to a maximum stress. It stores elastic energy per volume:

If it is loaded and then unloaded, it dissipates energy equivalent to the area of the stress-strain hysteresis
loop:

The loss coefficient is defined as

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The cycle can be applied in many different ways-some fact, some slow. The values of usually depend
on the tome-scale or frequency of cycling.
8. Creep: Time-dependent deformation which occurs when materials are loaded above 1/3Tm (melting
temperature). Examples: turbine blades, steam generators. it is then slow and permanent deformation
due to constant stress at high temperature for a long period of time. This property is very used in boilers,
turbines and internal combustion engines.
Final stage

Primary
stage

Secondary
stage

Elastic (instantaneous) deformation


Time

Fig.1.20: Creep testing and stages of creep time to deformation curve


1. Instantaneous deformation, mainly elastic.
2. Primary/transient creep. Slope of strain vs. time
decreases with time: work-hardening
3. Secondary/steady-state creep. Rate of straining is
constant: balance of work-hardening and recovery.
4. Tertiary. Rapidly accelerating strain rate up to
failure: formation of internal cracks, voids, grain
boundary separation, necking, etc.
Creep rate:

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With increasing stress or temperature:


- The instantaneous strain increases
- The steady-state creep rate increases
- The time to rupture decreases
The stress/temperature dependence of the
steady-state creep rate can be described by

Where Qc is the activation energy for creep, K2


and n are material constants =

Fig.1.22: Materials progressive creep at different temperature/stress in function of time


The creep strength of a material can be given as:
(i) the maximum stress that will cause less than the specified strain in a given time
(ii) the constant stress that will cause a specified secondary creep strain rate at constant temperature
Thermal fatigue: when the temperature of a material is repetitively increased and decreased
( acyclic change in temperature) thus generating high temperature gradients continuously, the
specimen will fail after a certain number of changes. It is caused by the inner temperature
differences causing stresses inside the material.
9. Technological (Production) properties: weldability, formability, castability, fabricationability,
hardenability, ease of manufacture, joining and finishing and machineability. Machineability may be
defined as property of metal, which indicates the ease with which it can be cut or removes by cutting
tools in various machining operations such as turning, milling.
The machinability of a material depends upon mechanical and physical properties of a metal, chemical
composition of a metal, microstructure of a metal and cutting condition. The following common metal
has machinability in the ascending order:

Not machinable: white cast iron

Very poor: sintered carbides, monel metal

Poor: high speed steel, wrought iron

Fair: low carbon steel, low alloy steel

Good: copper-aluminum alloy grey cast iron

Excellent: gun metal, zinc alloy, aluminum, magnesium alloy


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1.1.1.2 NON-MECHANICAL PROPERTIES


They are those properties which are possessed by a material and are not mechanical in nature. They are
thermal, optical, magnetic and electrical properties.
1. Thermal properties: Expansion, conductivity, thermal fatigue, thermal stress, thermal shock, latent
heat of fusion, etc
Thermal Conductivity: the ability of a material to transmit heat energy by conduction i.e. It is a
measure of heat flow through a material. It relates heat flow (the flow of heat energy per unit area
per unit time) to the temperature gradient (which describes a temperature difference per unit
distance), causing the heat flow. The rate at which the heat is conducted through a solid at steady
state Imeaning that the temperature profile does not change with time, i.e. the surface of the
material is always at the temperature T1 and the inside of the material at distance X is always at T2
throughout the experiment) is governed by thermal conductivity . It is measured by recording the
heat flux J(w?m2) flowing from surface at temperature T1 to ane at T2 in the material, separated by
a distance X.
(

Where

is the temperature gradient and is to be determined as a material specific constant

E.g.: soldering iron with a bit made of copper, the wooden handle remains cool as it has a low thermal
conductivity and resists to flow of heat energy.

Fig.: Soldering iron.


Expansivity (Thermal expansion coefficient, (1/k)): it is expansion of materials due to an
increase/decrease in temperature. Most materials expand when they are heated. The coefficient of
linear expansion is a measure of the amount by which a unit length of the material expands
(thermal strain) when its temperature is raised by 10C/10K. If the material is thermally isotropic, the
volumetric expansion per degree is 3. If working with a material which has a high value, the
cooling differences (ex: the surface cools more quickly) will create high inner stresses, which could
for example deform the shape of the material.
Thermal expansion (l) = x T x L; where is the thermal coefficient of linear expansion, l/l = x T,
therefore the stress = e x E = x T x E where E is the young modulus.
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Specific heat capacity Cp (at constant pressure:(J/KgK): the heat energy required to raise the
temperature of a unit mass (1kg) of the substance by one degree 10C (K) . It is measured by the
standard technique of calorimetry. E.g.: water requires more heat energy to raise its temperature
by any given amount than an equal mass of any other liquid; that is why water is used as a coolant.
Heat capacity (Cp), Q = mCpT
Specific heat = Cp/Atomic mass (Kg/Kg K)
Melting point, Tm: there are melting and recrystallization temperatures for all metals and alloys.
The melting point is the temperature at which a material turns from solid to liquid. Only pure
substances have a single melting temperature but alloys have a melting range of temperatures.
Usually, Tm for alloys is less that Tm of the parent metals
Fusibility: The ease with which materials will melt. Eg: Solder melts easily and so has a high fusibility
but fire bricks used for furnace linings only melt at very high temperatures, so they have low
fusibility such materials are called refractory materials and are used as thermal insulators (eg:
polystyrene).

Fig.: Solder and fire brick fusibility


Latent heat of fusion Lm: it is the heat (energy) required per unit mass to change a materials state
to another state i.e. from solid to liquid or from liquid to gas, thus process is reversible, therefore
includes a gas to liquid or from liquid to solid.
For pure metals this heat is absorbed at constant temperature (the melting temperature), Tm.
Amorphous solids (including many polymers) do not have the sharp Tm. When the change from a solid
state to fluid is over temperature range, it is not to define a latent heat of melting.
Recrystallization temperature: the approximate minimum temperature at which the deformed
crystal structure of a cold worked metal is replaced with a new crystal structure within specified
time.
Melting range: a temperature range where solid and liquid forms of an alloy exist together. For
various reasons it is better to have a small melting range.

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1200
1000

Melting
temperature of
the metal

Liquid

800

Melting range
(Cu)

600

Melting
temperature
of the alloy

(Ag)
0
Ag

10

20

Mass % Cu

90

100
Cu

Casting shrinkage: casting shrinkage is the sum of:


(a) Liquid shrinkage: the volume of the liquid decreases during cooling
(b) Solidification shrinkage: the volume of the material decreases during the transition from liquid
to solid state.
(c) Solid shrinkage: the volume of the solid decreases during cooling.
Casting shrinkage is high for materials with big thermal expansion coefficients. Casting shrinkage should
be considered when preparing moulds for casting, i.e. the mould should be prepared using bigger
dimensions that the wanted ones, as the product will shrink after casting.
Hot shortness: is a material and structural property which indicates the tendency of a material to
separate the grain boundaries when stressed near the melting temperature. It is usually caused by
a phase, which is not dissolved in the main phase, but it is located at the grain boundaries.
Temperature stability: substantial changes in temperature can have very significant effects on the
structure and properties of materials. There are two effects which changes in temperature can have
on the dimensional stability of a component:
- Thermal expansion: to a greater or less extent, all materials expand when heated and contract
when cooled.
- Creep: the gradual extension of a material over a long period of time whilst the applied load is
kept constant. It is important factor to consider in polymeric (plastic) materials, when metals
work continuously at high temperatures for eg: gas turbine blades.
Thermal shock resistance (k): maximum temperature difference through which a material can be
quenched suddenly without damage.
Maximum/minimum service temperature: they are highest/lowest temperatures at which a
material can reasonably be used without the effect of oxidation, chemical change or excessive
creep/ the loss of its original serviceable properties respectively.
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Glass transition temperature, Tg (k): a property of no-crystalline solids which do not have a sharp
melting point. It characterizes the transition from true solid to very viscous liquid in these materials.
Thermal diffusivity, a (m2/s): when the heat flow is not steady the flux depends on thermal
diffusivity
(

, where is the density and

the specific heat at constant pressure. It shows how quick

a heat, which is applied to the material, will be distributed among the material. At high and low
temperature differences will be equally quickly.
2. Electrical Properties: Resistivity, conductivity, dielectric constant, dielectric strength, relaxation time,
power factor. UI since U = I R but R = x L/A where : Resistivity, L: length, A: area.
Conductivity () = 1/ therefore R = L/ A
Electrical conductivity: property of materials to offer very little resistance to the flow of electrons
(electric current). Very bad conductors, such as PVC are called insulators.
Resistivity [10-8W.m] is the resistance offered by a unit cube of that material measured between
opposite faces. It describes the ability of a material to resist or oppose the transport of electrical
charge in response to an external electric field. It varies over a range: from 10-8W.m to more than
1016Wm for best insulators. The conductivity of metals and metal alloys improves as the
temperature falls. Conversely, non-metallic materials used for insulators become poorer insulators
with the temperature increase.

Fig.: Plastic insulator with copper wire conductor


Semiconductors: they lie in between conductors and insulators (e.g.: Silicon, germanium and certain
metal oxides). Their conductivity depends on their temperatures: it increases rapidly for relatively small
temperature increases. This enables them to be used as temperature sensors in electronic
thermometers and electronics industry (diodes, transistors and integrated circuits.
Breakdown potential [106V/m]: is the potential required to apply to a material that is normally an
insulator that allows conduction (or partial ionization) through the material. If the potential
gradient becomes too steep, normal conduction I replaced by electrical breakdown: a catastrophic
electron-cascade, usually causing permanent damage. Each insulator has a breakdown potential at
which the structure of the material is changed and therefore damaged to allow electric flow.
Dielectric constant: when a material (such as that used in capacitor) is placed in an electric field, It
becomes polarized and charges appear at its surfaces which tend to screen (separate) the interior
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Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy

from the external field. The tendency to polarize is measured by the dielectric constant. Dielectric
constant is the degree of polarization or charge storage capacity of a material when subjected to an
electric field.
Permittivity: (dimensionless) it is the ratio of electric flux density in the dielectric to the electric field
strength of the charge.
3. Magnetic properties: Hysteresis, retentivity, permeability, susceptibility, coercive force, reluctivity.
Reluctance: It is the resistance of a magnetic circuit. good conductors have a low reluctance. Eg is
ferromagnetic materials made from iron, steel and associated alloying elements such as cobalt and
nickel.
Permeability: (no unit) it is the ease with which a material can be magnetized. 0 r Where
, 0, r are the absolute, free space and relative permeabilities. It varies with the magnetizing force.

Fig.: Permeability vs magnetising force curves for some materials


Hysteresis: Magnetic materials subjected to alternating fields as in, say, a transformer core is
subjected to constantly changing conditions. They are magnetized in one direction, then
demagnetized, then magnetized again in another direction this cycle being repeated many times
per second depending upon the frequency of the magnetizing current. Magnetic materials require
time to adapt to these changes and tend to lag behind the current change. This lagging effect is
referred to as Hysteresis. The fatter the curve the greater the losses of energy which ends up as
heat. Hard magnetic materials are used in permanent magnets and soft magnetic materials are
used in transformer cores.

Fig.: Hysteresis curves for hard and soft magnets


4. Acoustical properties: materials to behave distinctly under sound exposure. They may exhibit sound

reflection, absorption, damping, transmission.

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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy

5. Optical properties: materials features when they encounter the light. Reflection, refraction,
transmission, fluorescence, luster, luminescence, etc

1.1. 2 CHEMICAL/ ENVIRONMENTAL PROPERTIES


Surface properties: Friction, porosity, abrasion and wear properties. It is included also oxidation and
corrosion properties.
Nuclear properties: half period, passivity, atomic number, etc.
Dry corrosion: it is the chemical reaction of a solid with dry gases. Typically a metal. M reacts with
oxygen and forms a surface layer of oxide.

If the oxide is protective, forming a continuous film without cracks over the surface, the reaction slows
don with time, as the oxygen cannot pass through this layer. The oxidation rate mainly depends on the
characteristic of this oxide layer, which can be describes by Pilling-Bedworth ratio.

Ao is the molecular weight of the metaloxyde, AM is the atomic weight of the metal, and are
corresponding densities.
If the Pilling-Bedworth ratio is smaller than 1, non-porous and protective oxide layer forms; If the ratio is
higher that 2 or 3 the layer breaks and is not protective any more
Flammability: Is a materials ability to suppress combustion. The number given as flammability
corresponds to a relative rating system, thus using it almost only for comparisons is reasonable.
Wet corrosion (caused by a reaction of metal with water, brine, acids and alkalis) is much more
complicated and cannot be defined by simple relations. It is more usually to scale the resistance by
relative values. Corrosion is effective in fresh water, organic solvents, sea water, strong acid, strong
alkalis, UV, weak acid and weak alkalis.
Metallurgical properties: phase rule, solid solution, crystallization rate, diffusion

1.1. 3 FACTORS AFFECTING MATERIALS PROPERTIES


The following are the more important factors which can be influence the properties and performance of
engineering materials.
1. Heat treatment
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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


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This is the controlled heating and cooling of metals to change their properties to improve their
performance or to facilitate processing. An example of heat treatment is the hardening of a piece of high
carbon steel rod. If it is heated to dull red heat and plunged into cold water to cool it rapidly (quenching),
it will become hard and brittle. If it is again heated to dull red heat but allowed to cold very slowly it will
become softer and less brittle (more tough). In this condition it is said to be annealed.
After the heat treatment happened on the material it will be in its best condition for flow forming,
during flow forming (working) the grains will be distorted and this will result in most metals becoming
Work hardened if flow formed at room temperature. To remove any locked in stresses resulting from
the forming operations and to prepare the material for machining, the material has to be normalized.
2. Processing
Hot and cold working process will be referred to understand what is meant by terms hot and cold
working as applied to metals. Figure below shows examples of hot and cold working.

Fig.: Examples of (a) hot-working and (b) cold-working process.


Metal is hot worked or cold worked depending upon the temperature at which it is flow formed to
shape. These temperatures are not easy to define. For instance, lead hot works at room temperature
and can be beaten into complex shapes without cracking, but steel does not hot work until it is red hot.
When metal are examined under the microscope it can be seen that they consist of very small grains.
When most metals are bent or worked at room temperature (cold worked) these grains become
distorted and the metal becomes hard and brittle. When metals are hot worked the crystals are also
distorted. However, they reform instantly into normal crystals because the process temperature is
above the temperature of recrystallisation for the metal being used and work hardening does not occur.
This cold working is the flow forming of metals below the temperature the recrystallisation, whilst hot
working is the flow forming of metals above the temperature of recrystallisation.
3. Environmental reactions
The properties of materials can also be affected by reaction with environment in which they are used.
For example:
Resting of steel: Unless steel structures are regularly maintained by rest neutralization and painting
process, resting will occur. The rest will eat into the steel; reduce its thickness and, therefore, its
strength. In extreme cases an entire structure made from steel may be eaten away.
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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


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Dezincification of brass: Brass is an alloy of copper and zinc and when brass is exposed to a marine
environment for along time, the salt in the sea water pray react with the zinc content of the brass so as
remove it and leave it behind on spongy, porous mass of copper. This obviously weakens the material
which fails under normal working conditions.
Degradation of plastic: Many plastic degrade and become weak and brittle when exposed to the
ultraviolet content of sunlight. Special dyestuffs have to be incorporated into the plastic to filter out
these harmful rays.

1.2 ENGINEERING MATERIALS SELECTION


1.2.1 INTRODUCTION
All engineering products utilize materials. The product demands for a material with specific
characteristics. To select the optimum material for engineering application, the understanding of the
material properties is essential. We can summarize different classes of properties that make a material
suitable for any engineering application as it follows:
1. Economic properties: Price and availability
2. Bulk mechanical properties: Density, modulus and damping, yield strength, tensile strength,
hardness, fracture toughness, fatigue strength, thermal fatigue resistance, creep strength.
3. Bulk non-mechanical properties: thermal, optical, magnetic and electrical properties.
4. Surface properties: friction, abrasion and wear; oxidation and corrosion.
5. Production properties: Ease of manufacture, fabrication, joining, finishing.
6. Aesthetic properties: Appearance, texture, feel.
1.2.2 PRINCIPLE OF MATERIAL SELECTION
The selection of a material for a particular application depends on several factors. The designer may
have to answer the following fundamental questions:

Does the material selected meet the strength requirements for the functioning of the design?

Is the material available at reasonable cost?

Can it be processed to the desired design shape and specifications?

Is the material safe to use?

Will the material survive the environment in which it is expected to operate?


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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


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Is it attractive?

At the end of its useful life, can it be recycled?

There are many factors to be considered when selecting, but broadly, one starts with broad range of
materials, and then narrows it down as some materials are eliminated. These factors are:
(a) Physical properties like: Size, shape and weight according to the available space, processing way,
energy consumption.
(b) Mechanical factors: they are used as design criteria to prevent mechanical failure, such as
tensile, yield, impact, creep strength, modulus of elasticity, etc.
(c) Processing and fabricability: How material will be processed of fabricated to the desired shape
and size. (Casted, forged, machined, welded, etc). The designer ought to know the heat
treatment and finish processing.
(d) Life of component factors: the expected life of the component. Factors related to the type of
loading and environment of operation are considered, such as corrosion, oxidation, wear,
impact loading, etc. Designers often develop life prediction model for estimating expected
design life.
(e) Cost and availability: this is because we live in a market driven economy. Cost of transportation
will make expensive materials that are not locally available.
(f) Codes, statutory and other factors: codes are sets of technical requirements imposed on the
material. They are set by the customer or standardization bodies (ISO, DIN, ASME, ASTM, SAE,
BS, etc.). Statutory factors relate to local, state, and federal regulations and relate to health,
safety and environment requirements.
What type of material should be used for a particular application? The choice depends on a number of
properties:
2.1. Bulk mechanical properties
Stiffness - resistance to bending and elastic deformation
Yield strength - point at which irreversible shape change occurs
Tensile strength - point at which the material becomes unstable and fracture is imminent
Hardness - resistance to abrasion
Ductility - the amount by which a material may be extended before failure occurs
Fracture toughness - the resistance to crack propagation, i.e. the opposite of brittleness
Fatigue resistance - as continual variations in stress can cause failure
Creep resistance - as there is a gradual extension of materials under stress with time.
Density - important when weight is of concern.
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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


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2.2 Surface properties


Oxidation resistance
Corrosion resistance
2.3 Non-mechanical properties
Thermal and electrical conductivity
Permeability
Magnetic properties; optical properties
2.4 Economic properties
Price
Availability
2.5 Production properties
Ease of manufacture (fabrication, welding etc.)
2.6 Other properties
Any environmental safety aspects
Appearance, texture, feel
Lets now consider two examples illustrating the basic requirements for selecting materials that are
suitable for a particular application.
Example1: A connecter joining electric cables (The plastic casing has been partly cut away to show the
metal connector). Plastic is used for the outer casing because it is a good electrical insulator and
prevents electric shock if a person touches it. It also prevents the conductors touching each other and
causing a short circuit. As well as being a good insulator the plastic is cheap, tough, and easily molded to
shape. It has been selected for the casing because of these properties that is, the properties of
toughness, good electrical insulation, and ease of moulding to shape. It is also a relatively low cost
material that is readily available.
The metal joining piece and its clamping screws are made from brass. This metal has been chosen
because of its special properties. These properties are good electrical conductivity, ease of extruding to
shape, ease of machining (cutting to length, drilling and tapping the screw threads), adequate strength
and corrosion resistance. The precious metal silver is an even better conductor, but it would be far too
expensive for this application and it would also be too weak and soft.

Fig.: The electrical connector.


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Example 2: The connecting rod of a motor car engine. This is made from a special steel alloy. This alloy
has been chosen because it combines the properties of strength and toughness with the ability to be
readily forged to shape and finished by machining.

Fig.: The connecting rod of motor car engine.


Selection of alloys for specific high temperature applications: Several factors involve in selection of
alloys for varying applications are as follow:
-

Expected life of the product


Temperature and stress to which it will be subjected
Corrosion characteristic of the alloy
Uniformity of temperature to which it is subjected
How often it is inspected
How much deformation is allowable if any
Hazards involved in case of failure
Availability and cost of alloy

Thus the reasons for selecting the materials in the above examples can be summarized as : Commercial
factors such as: Cost, availability, ease of manufacture and Engineering properties of materials such as:
Electrical conductivity, strength, toughness, ease of forming by extrusion, forging and casting,
machinability and corrosion resistance.

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2. CLASSIFICATION OF ENGINEERING MATERIALS


ENGINEERING MATERIALS

NON-METALLIC

METALLIC

FERROUS
Cast Iron
Malleable Iron
Wrought Iron

NON - FERROUS

MATERIALS DUE TO COMBINATION

Cooper,
Aluminum,
Magnesium,
lead, zinc, Tin

ORGANIC POLYMERS
COMPOSITES
Eg: stone, brick,
cement, rubber,
Metal Ceramic
plastics, glass,
etc.
Metal reinforced metal
Ceramic polymer

Steel

Polymer cement
concrete
Fig. 2.1: Classification of engineering materials

65

ALLOYS

CERAMICS

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FERROUS
Alloys containing
iron and steel

NON FERROUS
Alloys of
Aluminum,
Magnesium, lead,
zinc, Tin. Alloys of
Brass and Bronze
Brass (Cu + Zn),
Bronze (Cu + Sn,
Si, Be, Al, Ni)

Ferrous

Steel

Low/medium/high carbon steel and alloy steels

Cast Iron

Grey/white/malleable/high-duty C.I and alloy C.I

Wrought Iron

Metals

Metals

Al, Cd, Cr, Co, Cu, Au, Pb(lead), Mn, Mg, Mo, Ni, Pt, Ag(silver), Sn(tin), Ti, W, V, Zn
Brass (cu + Zn)

Non-ferrous

Tin bronze (cu + Sn)


Alluminium bronze (cu + Al)
Alloys

Cupro-nickel alloys (cu + Ni)

Phosphor bronze
Gun metal
Heat treatable (wrought)
Heat treatable (cast)

Alluminium alloys

Non-Heat treatable (wrought)


Non-Heat treatable (cast)
Zinc based die-casting alloys
Soft solders
Tin-lead alloys
Bearing metals
Thermoplastic Acrylic, PTFE, polythene, PVC (polyvinyl chlorine), nylon, olystyrene

Magnesium alloys

E.M

Plastics
Synthetic
Non-Metals
Natural

66

Thermosetting

Epoxides, Alkyds, phenoi/melanine/Urea-formaldehydes

Ceramics

Glass, Porcelain, cemented carbides

Composites

Carbon fibre, concrete, glass reinforced plastic (GRP)

Asbestos, colourants (dies & pigments), Coal, Cotton, Diamond, Emery, Gases (Ar, Methane, Ne, Ni,
O, He: air derivatives), Glues: animal derivatives, Gums: vegetable derivatives, granite, Mica, Oil,
Quartz, Rubber, Sapphire, Wood, Wool

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Fig.2.2: Simplified classification of materials

2.1 OVERVIEW ABOUT METALS AND ALLOYS


They are inorganic materials composed of one or more metallic elements. Metals are elementary
substances strong, yet capable of changing their shape permanently under applied mechanical loads.
They are good conductors of heat and electricity and opaque to light (shiny if polished). These
characteristics are due to valence electrons that are detached from atoms, and spread in an
electron sea that glues the ions together, i.e. atoms are bound together by strong metallic bonds and
weaker van der Waalls forces.
Structurally, atoms in metals normally adopt one of three common arrangements: hexagonal closepacked (HCP, stacking arrangement ABABAB), cubic close-packed (FCC, stacking arrangement ABCABC)
or body centered cubic (BCC). The valence electrons occupy a conduction band, which means that they
are delocalized throughout the structure (accounting for the high thermal and electrical conductivity of
metals). Hence, pure metal objects are used where good electrical and thermal conductivity,
good corrosion resistance or a combination of these properties are required; nonetheless, they are
not good enough for many applications, especially structural applications necessitating superior
mechanical properties. Thus metals are mixed up with other additional metals (E.g.: aluminum, steel,
brass, gold) to fill up their lack in desired properties that are dependent on various working spectrum.
Such a combination is termed alloy. By virtue of composition, they are often grouped into two classes
ferrous and nonferrous:
2.1.1 Ferrous metals: wherein iron is the prime component with a light but influential carbon
concentration; reason why sometimes they are referred to as alloys. They are under two types: steels
and cast irons and are produced in larger quantities than any other metal type and quite important as
engineering construction materials.

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METAL ALLOYS

FERROUS
Steels

Cast irons

Low alloys

Low-carbon

Plain

Medium-carbon

High strength Plain


Low alloy

NONFERROUS

High alloys
Gray Ductile White Malleable
iron (nodular) iron iron
iron

High-carbon

Heat
Plain
treatable

Tool

Compacted
graphite
iron

Stainless

Fig.: Classification scheme for various ferrous alloys.


Their behaviour and properties preponderantly depend on the slight percentage component and the
form (phase and constituents) of carbon hinged in them.
Table: The difference btn Steel and Iron and their specific names according to percentage of carbon.
% of C

Specific names

Purest to 0.05

Wrought iron

0.05 to 0.15

Dead mild steel

Pressed steel body


panel

0.15 to 0.30

Mild steel

Steel rod and bars

0.30 to 0.70

Medium carbon steel

Forgings

0.70 to 1.40

High carbon steel

Springs, drills, chisels

1.40 to 2.00 (1.7)

Semi-steel or semi-iron

2.00 (1.7) to 4.50

Cast iron (Grey, white,


mottled, spongy, malleable,
chilled, spheroidal, nodular)

4.50 to 6.67

Pig iron

6.67 or more

Ore

68

Typical applications

Steel or Cast Iron


Plain carbon steel

Engine blocks

Cast Iron

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2.1.2 Non-Ferrous metals: they do not contain Fe and C as their constituents. Al, Cu, Ag, Au are good
conductors of electricity. Ag is most malleable, Au is most ductile and Chromium is corrosion resistant.
Zinc is used in metal plating, Tin is used to make bushes and Nickel imparts strength and creep
resistance.
Major properties of metals are:

They usually have a crystalline structure and are good thermal and electrical conductors
Many metals have high strength and high elastic module
They maintain their good strength at high and low temperatures
They also have sufficient ductility, which is important for many engineering applications
They can be strengthened by alloying and heat treatment

2.1.3 Alloys: Pure metals are rarely used in structural applications as alloys allow mechanical properties
to be tailored to meet particular requirements since they possess properties quite different from those
of their constituent metals. They are combination of two or more metals whether non ferrous or ferrous
(ferrous alone can be considered as alloys of Fe and C). Alloys are normally treated as solid solutions
of two metals. In some cases the atoms of the second metal occupy the sites normally occupied by the
first metal (a substitutional solid solution, e.g. brass, up to 30% zinc in copper); in others, the atoms of
the second metal occupy the gaps between the atoms of the first metal. They are found under ferrous
and non ferrous alloys depending on their base metal. The ferrous alloys are particularly important
materials, and these are broadly classed into: irons, containing <0.015 % carbon, steels, cast irons. Steels
themselves are normally described as:
Carbon steels (or mild steels). These contain just iron and some carbon, and have excellent mechanical
properties at moderate temperatures (but not necessarily at high temperatures). They also have poor
corrosion resistance. Carbon steels are cheap, readily available and easy to fabricate.
Stainless steels. There are a whole range of stainless steels containing different amounts of nickel and
chromium as well as other additives for special purposes. They are subdivided according to their
metallurgical structure, which depends on their chemical composition:
Ferritic: 13-20 % Cr ; no Ni ; <0.1 % C; Austenitic: 18-20 % Cr ; >7 % Ni ; variable C; Martensitic: 10-12 %
Cr ; <2 % Ni ; 0.2-0.4 % C
Austenitic steels are particularly important in the chemical industry due to their excellent corrosion
resistance (caused by a CrO2 layer at the surface).
Other types of steel which are intermediate in character between the carbon steels and stainless
steels for particular applications are: Low alloy steels: these contain up to 2.5 % chromium and
molybdenum; Chrome steels: these contain up to 12 % chromium; Nickel steels: these contain up to 9 %
nickel.
Other metal alloys that are widely used are those of alluminium, copper, nickel and titanium.

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2.2 INTRODUCTION TO NON METALLIC MATERIALS


Non metallic (Natural materials)
Such materials are so diverse that only a few can be listed here to give a basic introduction to some
typical applications.
Wood: Naturally occurring fibrous composite material used for the manufacture of casting patterns.
Rubber: used for hydraulic, compressed air hoses and oil seals. Naturally occurring latex is too soft
for most engineering uses but used widely for vehicle tyres when compounded with carbon black.
Glass: This is a hardwearing, abrasion-resistant material with excellent weathering properties. It is
used for electrical insulators, laboratory equipment, optical components in measuring instruments,
in the form of fibers, is used to reinforce plastics. It is made by melting together the naturally
occurring materials: silica (sand), limestone (calcium carbonate) and soda (sodium carbonate).
Emery: This is a widely used abrasive and is a naturally occurring aluminum oxide. Nowadays it is
produced synthetically to maintain uniform quality and performance.
Ceramic: Produced by baking naturally occurring clays at high temperatures after moulding to shape.
They are used for high voltage insulators and high temperature resistant cutting tool tips.
Diamonds: These can be used for cutting tools for operation at high speeds for metal finishing
where surface finish is greater importance. For example, internal combustion engine pistons and
bearings. They are also used for dressing grinding wheels.
Oils: Used as bearing lubricants, cutting fluids and fuels.
Silicon: This is used as an alloying element and also for the manufacture of semiconductor devices.
These and other natural, non-metallic materials can be classified as shown in figure
Asbestos
Colourants
Coal

Dyes
Pigments

Cotton
Diamond
Emery

)
(

Gases
}

Natural materials
Glues (animal derivatives)
Gums (Vegetable derivatives)
Granites
Mica
Oil
Quartz
Rubber
Sapphire
Wood
Wool
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2.2.1 POLYMERS
In Greek mer means a unit poly means manyPolymer = many units; Mono: one. Materials
generally known as plastics and rubbers are built up from (normally organic) monomeric building units
that bring about long molecular chains or networks.
We know that many organic materials are hydrocarbons; that is, they are composed of hydrogen and
carbon. Furthermore, the intermolecular bonds are covalent. Each carbon atom has four electrons that
may participate in covalent bonding, whereas every hydrogen atom has only one bonding electron. The
hydrocarbon molecules in polymers are comparatively gigantic often referred to as macromolecules in
which monomers (individual molecules) are linked up/bonded by chemical reaction through a process
named polymerization to form polymers.
Polymerization:
Ethylene (C2H4) is a gas at room temp and pressure but it transform to polyethylene (solid) by forming
active mer through reaction with initiator or catalytic radical (R).
1. Initiation reaction
(.) denotes unpaired electron (active site)
2. Rapid propagation ~1000 mer units in 1-10 ms
3. Termination when two active chain ends meet
each other or active chain end meet with initiator
or other species with single active bond
Replace hydrogen atoms in polyethylene:
polytetraflouroethylene (PTFE) Teflon

make

Replace every fourth hydrogen atom in polyethylene with


Cl atom: polyvinyl chloride

Replace every fourth hydrogen atom in polyethylene with


CH3 methyl group: polyproplylene
if monomers are of the same kind or co-polymers if different monomers are joined together in a regular
pattern (e.g.: polyvinyl chloride that has alternate molecules of vinyl chloride and vinyl acetate). In
polymerization process, long molecular chain having high molecular weight is generated: Bakelite,
polyethylene, nylon, Teflon are some example. Long-chain polymers are usually weaker than most

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ceramics and metals because the molecular chains are bonded to each other with only rather than weak
electrostatic forces called Van der Waals bond.
Copolymers, polymers with at least two different types of mers, can differ in the way the mers are
arranged

Fig.: Synthetic rubbers are copolymers


Polymers may be natural, such as cellulose or DNA, or synthetic, such as nylon or polyethylene. Silk fibre
is produced by silk worms in a cocoon, to protect the silkworm while it metamorphoses in a moth. Living
organisms are mainly composed of polymerized amino acids (proteins) nucleic acids (RNA and DNA), and
other biopolymers. The most powerful computers -our brains - are mostly just a complex polymer
material soaking in salty water.
Naturally occurring polymers i.e. those derived from plants and animals have been used for many
centuries; these materials include wood, rubber, cotton, wool, leather, and silk. Other natural polymers
such as proteins, enzymes, starches, and cellulose are important in biological and physiological
processes in plants and animals. Many of our useful plastics, rubbers, and fiber materials are synthetic
polymers with and advantage to be produced inexpensively, and their properties may be managed to
the degree that many are superior to their natural counterparts.
2.2.1.1 The microstructure of polymers
When metals solidify we see a crystalline structure form as the small molecules move easily into regular
shapes with ionic bonds holding them together. Polymers have long chain molecules entangled with
each other and this makes it difficult for them to move and form a crystalline pattern. The solidification
process of polymers may produce some regions in crystalline form and these are called crystallites. The
rest of the material is amorphous, except for a minority of thermoplastics. The crystalline region can be
as much as 90% in some polymers. Thence, most polymers are non-crystalline, but some consist of
mixtures of both crystalline and non-crystalline regions: The long-flexible chains may be arranged
completely randomly (giving an amorphous polymer) or in a regular chain-folding pattern (leading to
crystalline regions within the polymer)
A polymer has a repeating structure, usually based on a carbon backbone. The repeating structure
results in large chainlike molecules. In each polymer molecule, the hydrocarbon atoms are bound
together by strong covalent bonds. However, the bonding between chains is far weaker (Van der Waals
type).

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Fig.: Polymeric structure and covalent bonding


Double and triple bonds can exist between C atoms (sharing of two or three electron pairs). These bonds
are called unsaturated bonds. Unsaturated molecules are more reactive. Isomers are molecules that
contain the same atoms but in a different arrangement. An example is butane and isobutane:

Two types of isomerism are possible: stereoisomerism (atoms are linked together in the same order,
but can have different spatial arrangement) and geometrical isomerism (consider two carbon atoms
bonded by a double bond in a chain. H atom or radical R bonded to these two atoms can be on the same
side of the chain (cis structure) or on opposite sides of the chain (trans structure).

Fig.: Cis-polyisoprene and Trans-polyisoprene

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Isotactic configuration: all side groups R are


on the same side of the chain.

Syndiotactic configuration: side groups R


alternate sides of the chain.

Atactic configuration: random orientations of


groups R along the chain.
Fig.: Stereoisomerism
R represent radical, an organic group of atoms that remain as a unit and maintain their identity during
chemical reactions (e.g. CH3, C2H5, C6H5)
The detailed properties of a particular polymer will depend on factors such as chain length, crystallinity
and the presence of any crosslinking between the chains. The physical characteristics of a polymer
depend not only on its molecular weight and shape but also on differences in the structure of the
molecular chains. Each circle represents a repeat unit

Fig.: possible molecular structures over covalent chain configurations with strength increasing from
left to right.
Linear Polymers: repeating units are joined together end to end in single chains. These long chains are
flexible. For linear polymers, there may be extensive van der Waals and hydrogen bonding between the
chains. Some of the common polymers that form with linear structures are polyethylene (synthetic
polymer: a plastic polymer of ethylene. Use: manufacture of containers, packaging, and electrical
insulation), polyvinyl chloride (PVC), polystyrene, polymethyl methacrylate (plexiglass), nylon, and the
fluorocarbons (Teflon)
Branched Polymers: synthesized so that side-branch chains are connected to the main ones and
considered to be part of the main chain molecule. They result from side reactions that occur during the
synthesis of the polymer. The chain packing efficiency is reduced with the formation of side branches,
which results in a lowering of the polymer density. Those polymers that form linear structures may also
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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


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be branched. For example, high density polyethylene (HDPE) is primarily a linear polymer, while low
density polyethylene (LDPE) contains short chain branches.
Cross-linked Polymers: adjacent linear chains are joined one to another at various positions by covalent
bonds. The process of cross linking is achieved either during synthesis or by a nonreversible chemical
reaction. Often, this cross linking is accomplished by additive atoms or molecules that are covalently
bonded to the chains. Many elastomers or polymeric rubbers are cross-linked (vulcanization process);
most thermosetting polymers
Network (3D molecular structure) Polymers: Multifunctional monomers forming three or more active
covalent bonds make three-dimensional networks. Actually, a polymer that is highly cross linked may
also be classified as a network polymer. These materials have distinctive mechanical and thermal
properties; the epoxies, polyurethanes, and phenol-formaldehyde belong to this group.
Polymers are not usually of only one distinctive structural type. For example, a predominantly linear
polymer might have limited branching and cross linking.

2.2.1.2 Polymers classification


Polymers can be classified into two groups:

Plastics: Possibly the largest number of different polymeric materials come under the plastic

classification. Plastics are materials that have some structural rigidity under load, and are used in
general-purpose applications. Polymers falling within this classification may have any degree of
crystallinity, and all molecular structures and configurations (linear, branched, etc.) are possible.
However, to be considered plastics, linear or branched polymers must be used below their glass
transition temperatures (if amorphous) or below their melting temperatures (if semicrystalline), or
must be cross linked enough to maintain their shape.
The advantages underlying plastics that propel their increased use are: their many useful properties,
couples with comparatively low cost, their low densities, their high resistance to chemical attack, their
thermal and electrical insulation properties, their ease of fabrication in to a wide variety of both simple
and complex shapes. However, they exhibit following vices: The low strength and elastic modulus
values, in compression with those of metals; the low softening and thermal degradation temperature;
their comparatively high thermal expansion coefficients.
Plastic materials may be either thermoplastic or thermosetting as sub-classification:
Thermoplastic: Heating the polymer vibrates the molecules and if they are not cross linked, the distance
between the molecules will increase and the Van der Waal forces will be reduced. This will make the
polymer soften so these types and be remoulded by heating. Thermo-plastics (nylon, polyethylene,
polyvinyl chloride, rubber, etc.) consist of molecules that have covalent bonding within each molecule
and van der Waals forces between them.
Thermosetting: During the moulding process, chemical changes occur and the molecules become cross75

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linked forming a more rigid structure. Reheating will not soften the polymer. Thermo-sets (e.g., epoxy,
phenolics, etc.) consist of a network of covalent bonds. are relative inert and light, generally have a
high degree of plasticity, so named plastics.
Thermoplastics
Thermosets
Softened when heat treated and harden Become permanently hard after the initial
when cooled
heat-cooling cycle
Varying degree of ductility

Brittle

Can be recycled

Cannot be recycled

Cannot withstand high temperatures

Can withstand high temperatures

Elastomers/Rubber (elastic mers): These are virtually the same as thermosetting but they have a
very high degree of elasticity (elongates on stretching and regains its original shape after removal
the stress) and although they stretch easily compared to metals, they spring back into shape. The
tangled molecules tend to straighten when pulled but spring back when released.

Elastomers are long polymer chains above their glass transition temperature (a property of nocrystalline solids which do not have a sharp melting point). Polymers are generally soft at normal
temperatures but they can become hard and brittle when cooled. The temperature at which they
change from soft and flexible to hard and glassy, is called the glass transition temperature denoted T g.
Some polymers are hard and rigid at normal temperatures and these have many uses.

Fig.: The stress-strain behavior for brittle (A), plastic curve (B) and highly elastic/elastomeric polymers
(C) and a schematic tensile stress-strain curve for a semicrystalline polymer wherein Specimen
contours at several stages of deformation are included.
Curve A illustrates a brittle polymer, inasmuch as it fractures while deforming elastically. The behavior
for a plastic material, curve B is similar to that for many metallic materials; the initial deformation is
elastic, which is followed by yielding and a region of plastic deformation. Finally, the deformation
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displayed by curve C is totally elastic; this rubber-like elasticity (large recoverable strains produced at
low stress levels) is displayed by a class of polymers termed the elastomers.
Elastomeric polymer chains can be crosslinked, or connected by covalent bonds. This process is
sometimes called vulcanization. Crosslinking is initiated by heat, light, or the addition of chemicals.
Crosslinking makes elastomers reversibly stretchable for small deformations. When stretched, the
polymer chains become elongated and ordered along the deformation direction. When no longer
stretched, the chains randomize again. The crosslinks guide the elastomers back to its original shape.
Returned to randomization
stretched

Fig.: Crosslinking makes elastomers reversibly stretchable for small deformations.


Common elastomers include: Polybutadiene (used in shoe soles); Polyisobutylene (used in automobile
tires); Polyisoprene (natural rubber).
The rubbers may contain a large number of constituents such as sulfur, accelerators,, (i.e., catalysts like
lime, magnesia, litharge, ect) antioxidants (negative catalysts like complex organic compounds),
reinforcing agents (like carbon black, zinc oxide ect.) coloring agents like zinc sulphide, lead chromate
etc.) And plasticizers like oils, stearic acid etc.) these constituents are added to the polymers to obtain
certain desirable properties in them. These properties include elasticity, tensile strength, resistance
against chemical reagents, and resistance to abrasion, low electrical and thermal conductivity.
The structure of rubber consists of long chain molecules which are interlocked with one another. It has
been observed that when a tensile stress is applied to a rubber molecule, the chain gets stretched and
considerable elongation takes place. On removing the stress, the thermal agitation will return the chain
to the interlocked form, thus causing the rubber to return to its original length.
2.2.1.3 General properties of polymers
Polymers are often referred to as plastics because their majority often has a very large plastic range i.e.
high degree of plasticity. Polymers exhibit a wide range of mechanical properties (strength, toughness
and hardness etc.) They have a low rigidity and low density compared to other materials and so for
example, a plastic bottle is much lighter than a glass bottle of equivalent strength. They can be colored
or transparent and give a pleasing finished appearance to many household items. These properties
make them suitable for a wide range of manufactured items such as:
Plastic tubes/pipes; Bottles; Car shells/interior linings; Cases for electronic goods; Springs/shock
absorbers; Tool handles/cases; Toys; Electric wire insulation; Seals used in hydraulics and pneumatics;
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Packaging; Linings to vessels.


Polymers three distinctive properties are to be stressed on:
Electrical insulation: Due to the kind of bonding, polymers are typically electrical insulators; however,
their usefulness in this field is limited by their low heat resistance [decompose at moderate
temperatures (100400C)] and their softness hence outdoors weather sensitivity. Conducting polymers
can be obtained by doping, and conducting polymer-matrix composites can be obtained by the use of
conducting fillers.
Corrosion resistance: All polymeric materials are inert to most inorganic chemicals i.e. very resistant to
attack from chemicals reagents and can be used in environments which are hostile even to the most
corrosion-resistant metals. The synthetic rubbers, which are a product of polymer chemistry, are
superior to natural (Polyisoprene) since they are not attacked by oils and greases.
Strength/weight ratio: Some of the stronger, such as nylon, compare favorably with the weaker metals.
All polymeric materials are much lighter than any of the metals used for engineering purposes.
Therefore, properly chosen and proportioned, their strength/weight ratio compares favorably with
many light alloys and they are steadily taking over engineering, duties which, until recently, were
considered the prerogative of metal.
Plasticity: They have a wide variety of combinations of properties: Some plastics are very rigid and
brittle (curve A). Others are flexible, exhibiting both elastic and plastic deformations when stressed, and
sometimes experiencing considerable deformation before fracture (curve B). Several plastics exhibit
especially outstanding properties. For applications in which optical transparency is critical, polystyrene
and poly (methyl methacrylate) are especially well suited; however, it is imperative that the material be
highly amorphous or, if semicrystalline, have very small crystallites. The fluorocarbons have a low
coefficient of friction and are extremely resistant to attack by a host of chemicals, even at relatively high
temperatures. They are utilized as coatings on nonstick cookware, in bearings and bushings, and for
high-temperature electronic components.
Mechanical properties for polymers vary greatly. The mechanical features of polymers, for the most
part, are highly sensitive to the rate of deformation (strain rate), the temperature, and the chemical
nature of the environment (the presence of water, oxygen, organic solvents, etc.).
It is important to determine the properties of polymeric materials which are ranged from highly plastic
to the highly elastic. As in figure the stress-strain curves for polymeric materials have been classified in
to five main groups by Carswell and Nason.

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Fig.: Typical stress-strain curves for polymers.


Other physical properties vary greatly:
Composed of very large molecules; Low modulus of elasticity (low stiffness); Low tensile and
compressive strengths; Can be crystalline or semi-crystalline structure; Deformation is very sensitive to
temperature; Low thermal and electrical conductivity (good insulator); Creep at room temperatures;
Low temperatures make plastics brittle; Plastic deformation.
2.2.1.4 Melting of polymers and their processing Methods
Metals and other crystalline materials melt at a fixed temperature but amorphous materials tend to
soften and become more like a viscous liquid. If a polymer has a large crystalline content, the change
from crystalline to amorphous structures when it melts is accompanied by an increase in the volume.
The temperature at which this occurs is denoted Tm. Generally, the melting point increases in
temperature with the degree of crystallinity.
Polymers are formed by many low temperature processes.
Extrusion: The polymer is heated to the liquid state and forced through a die under pressure
resulting in an endless product of constant cross section. 60% of polymers are prepared in this
way. Examples: tubing, pipes, window frames, sheet, insulated wire
Film Blowing: Using the same method as extrusion the material coming out of the die is blown
into a film. An example is plastic wrap.

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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


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Injection Molding: Similar to extrusion, the polymers heated to the liquid state, but it is
prepared in metered amounts, and the melt is forced into a mold to create the part. It is not a
continuous process. Many toys are made by injection molding
Blow Molding: The melted polymer is put into a mold, and then compressed air is used to
spread the polymer into the mold. It is used to make many containers such as plastic soda
containers and milk jugs.
Compression Molding: Solid polymer is placed in a mold; the mold is heated and puts pressure
on the polymer to form the part.
Reaction Injection Molding: Liquid monomers are placed in the mold avoiding the need to use
temperature to melt the polymer or pressure to inject it. The monomers polymerize in the mold
forming the part.
Industrially Important Polymers
About 85% of the world plastics consumption consists of four polymers. These polymers are produced in
high volume at very low cost. They are all thermoplastics.
Polyethylene (PE): electrical wire insulation, flexible tubing, squeeze bottles
Polypropylene (PP): carpet fibers, ropes, liquid containers (cups, buckets, tanks), pipes
Polystyrene (PS): packaging foams, egg cartons, lighting panels, electrical appliance components
Polyvinyl chloride (PVC): bottles, hoses, pipes, valves, electrical wire insulation, toys, and
raincoats.
Examples of important polymers are polyethylene (PE), polymethylmethacrylate (PMMA, perspex),
nylon, polystyrene (PS), polyurethane (PU) and polyvinylchloride (PVC).

2.2.2 CERAMICS
The word ceramic is traced to the Greek term Keramos, meaning pottery or potter. Ceramics are
compounds between metallic and nonmetallic elements with a crystalline structure, usually processed
at a high temperature at some time during their manufacture. They are most frequently oxides, nitrides,
and carbides. For example, some of the common ceramic materials include aluminum oxide (or alumina,
Al2O3), silicon dioxide (or silica, SiO2), silicon carbide (SiC), silicon nitride (Si3N4), 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. Initially termed traditional ceramics, are those for which the primary raw material
is clay; products considered to be traditional ceramics are china, porcelain, bricks, tiles, and, in addition,
glasses and high-temperature ceramics. Of late, significant progress; a new generation of these
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materials has evolved, and the term ceramic has taken on a much broader meaning (electronic,
computer, communication, aerospace, and a host of other industries rely on their use). Several common
ceramic objects are:

Fig.: Common objects that are made of ceramic materials: scissors, a china tea cup, a building brick, a
floor tile, and a glass vase.
Types and Applications of Ceramics:
Most ceramic materials fall into an application-classification scheme that includes the following groups:
CERAMIC MATERIALS

Glasses

Clay products

Refractories

Abrasives

Cements

Advanced ceramics

Fig.: Classification of ceramic materials on the basis of application.


1) Glasses: The glasses are a familiar group of ceramics; containers, lenses, and fiberglass represent
typical applications. Most inorganic glasses can be made to transform from a noncrystalline state to one
that is crystalline by the proper high-temperature heat treatment. This process is called crystallization,
and the product is a fine-grained polycrystalline material which is often called a glassceramic. The
formation of these small glass ceramic rains is, in a sense, a phase transformation, which involves
nucleation and growth stages.
Glass-ceramic materials have been designed to have the following characteristics: relatively high
mechanical strengths; low coefficients of thermal expansion (to avoid thermal shock); relatively high
temperature capabilities; good dielectric properties (for electronic packaging applications); and good
biological compatibility.
The most common uses for these materials are as ovenware, tableware, oven windows, and
rangetopsprimarily because of their strength and excellent resistance to thermal shock. They also
serve as electrical insulators and as substrates for printed circuit boards, and are used for architectural
cladding, and for heat exchangers and regenerators.
2) Clay Products
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One of the most widely used ceramic raw materials is clay. This inexpensive ingredient, found naturally
in great abundance, often is used as mined without any upgrading of quality. Another reason for its
popularity lies in the ease with which clay products may be formed; when mixed in the proper
proportions, clay and water form a plastic mass that is very amenable to shaping. The formed piece is
dried to remove some of the moisture, after which it is fired at an elevated temperature to improve its
mechanical strength.
3) Refractories
Another important class of ceramics that are utilized in large tonnages is the refractory ceramics. The
salient properties of these materials include the capacity to withstand high temperatures without
melting or decomposing, and the capacity to remain unreactive and inert when exposed to severe
environments. In addition, the ability to provide thermal insulation is often an important consideration.
Refractory materials are marketed in a variety of forms, but bricks are the most common. Typical
applications include furnace linings for metal refining, glass manufacturing, metallurgical heat treatment,
and power generation. Of course, the performance of a refractory ceramic, to a large degree, depends
on its composition. On this basis, there are several classifications namely, fireclay, silica, basic, and
special refractories.
4) Abrasives
Abrasive ceramics are used to wear, grind, or cut away other material, which necessarily is softer.
Therefore, the prime requisite for this group of materials is hardness or wear resistance; in addition, a
high degree of toughness is essential to ensure that the abrasive particles do not easily fracture.
Furthermore, high temperatures may be produced from abrasive frictional forces, so some
refractoriness is also desirable.
Diamonds, both natural and synthetic, are utilized as abrasives; however, they are relatively expensive.
The more common ceramic abrasives include silicon carbide, tungsten carbide (WC), aluminum oxide
(or corundum), and silica sand.
5) Cements
Several familiar ceramic materials are classified as inorganic cements: cement, plaster of paris, and lime,
which, as a group, are produced in extremely large quantities.
The characteristic feature of these materials is that when mixed with water, they form a paste that
subsequently sets and hardens. This trait is especially useful in that solid and rigid structures having just
about any shape may be expeditiously formed. Also, some of these materials act as a bonding phase
that chemically binds particulate aggregates into a single cohesive structure. Under these circumstances,
the role of the cement is similar to that of the glassy bonding phase that forms when clay products and
some refractory bricks are fired. One important difference, however, is that the cementitious bond
develops at room temperature.

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6) Advanced Ceramics
Many of our modern technologies utilize and will continue to utilize advanced ceramics because of their
unique mechanical, chemical, electrical, magnetic, and optical properties and property combinations.
General Properties
With regard to mechanical behavior, ceramic materials are relatively stiff and stiffnesses and strengths
are comparable to those of the metals. In addition, ceramics are typically very hard. On the other hand,
they are extremely brittle (lack ductility), and are highly susceptible to fracture. These materials are
typically insulative to the passage of heat and electricity, and are more resistant to high temperatures
and harsh environments than metals and polymers.
Ceramic materials are somewhat limited in applicability by their mechanical properties, which in many
respects are inferior to those of metals.
Brittle Fracture of Ceramics: The brittle fracture process consists of the formation and propagation of
cracks through the cross section of material in a direction perpendicular to the applied load. Crack
growth in crystalline ceramics may be either transgranular (i.e., through the grains) or intergranular (i.e.,
along grain boundaries); for transgranular fracture, cracks propagate along specific crystallographic (or
cleavage) planes, planes of high atomic density.
StressStrain Behavior: At room temperature, virtually all ceramics are brittle. Microcracks, the
presence of which is very difficult to control, result in amplification of applied tensile stresses and
account for relatively low fracture strengths (flexural strengths). This amplification does not occur with
compressive loads, and, consequently, ceramics are stronger in compression. The stress at fracture using
this flexure test is known as the flexural strength, modulus of rupture, fracture strength, or the bend
strength, an important mechanical parameter for brittle ceramics.
Hardness: One beneficial mechanical property of ceramics is their hardness, which is often utilized when
an abrasive or grinding action is required; in fact, the hardest known materials are ceramics.
Creep: Often ceramic materials experience creep deformation as a result of exposure to stresses (usually
compressive) at elevated temperatures. In general, the time deformation creep behavior of ceramics is
similar to that of metals; however, creep occurs at higher temperatures in ceramics. High temperature
compressive creep tests are conducted on ceramic materials to ascertain creep deformation as a
function of temperature and stress level.

2.3 COMPOSITES
2.3.1 INTRODUCTION
These are inorganic or organic, chiefly man-made materials made up from, or composed of, a
combination of different materials (Metal and ceramics, metal and polymers, ceramics and polymers or
others) on macroscopic level to take overall advantage of their improved or modified dissimilar
properties. Material property combinations and ranges have been extended by the development of
composite materials. Such a deliberate combination was understood by ancient civilizations. An example
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of this was the reinforcement of air-dried bricks by mixing the clay with straw so as to reduce cracking
caused by shrinkage stresses as the clay dried out. In more recent times, horse hair was used to
reinforce the plaster used on the walls and ceiling of buildings in order to reduce the onset of drying
cracks.
According to this principle of combined action, better property combinations are fashioned by the
judicious combination of two or more distinct materials. Property trade-offs are also made for many
composites.
Nowadays, especially with the growth of the plastics industry and the development of high-strength
fibers, a new generation of extraordinary materials with vast range combinations of materials is
available for use . For example, carbon fiber reinforced frames for tennis rackets and shafts for golf clubs
have revolutionized these sports.
Most composites have been created to improve combinations of mechanical characteristics such as
stiffness, toughness, and ambient and high-temperature strength.
In a 'composite', the reinforcement material, in the form of rods, strands, fibers or particles, is bonded
together with the other matrix materials. For example, the fibers may have some of the highest moduli
and greatest strengths available in tension, but little resistance to bending and compressive forces. On
the other hand, the matrix can be chosen to have high resistance to bending and compressive forces.
Used together these two different types of material produce a composite with high tensile and
compressive strengths and a high resistance to bending
Moreover, Alloys of metals with non-metals could only occur if all the component materials were
miscible, that is, soluble in each other in the molten state. Composite materials can be made up from
materials that are not soluble in each other. Composite materials are not alloys. In its simplest form a
composite material consists of two dissimilar materials in which one material forms a matrix to bond
together the other (reinforcement ) material. The matrix and reinforcement (fibrous form or flake form)
are chosen so that their mechanical properties complement each other, whilst their deficiencies are
neutralized. For example, in GRP molding, the polyester resin is the matrix that binds together the glass
fiber reinforcement.
Generally speaking, a composite is considered to be any multiphase material that exhibits a significant
proportion of the properties of both constituent phases such that a better combination of properties is
realized.

2.3.2 COMPOSITES CLASSIFICATIONS


Polymers are broadly two categories.
2.3.2.1 Particle reinforcement composites
This is a material in which particles of one material is fixed in a matrix of another. Here are
some examples.
(a) Cermets (ceramics and metals) - Particles of very hard ceramic materials are embedded in a metal
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to produce cutting tools and dies. For example, tungsten carbide embedded in cobalt makes a very
hard cutting tool and dies. They can be compacted into the required shape and then heated to
sinter them.( cobalt is hot enough to re-crystallize and form a matrix around the tungsten).
(b) Mortar and Concrete: mortar made from a hydraulic cement and sand reinforced with an
aggregate of chipped stones. Sand, gravel and stone are bonded into a matrix of cement that sets
and forms a light material strong in compression. Since it can be molded or laid down wet, it is an
ideal building material. The stones are crushed so that they have a rough texture and sharp corners
that will key into and bond with the mortar matrix. This basic concrete has a very high compressive
strength but is very weak in tension.

Fig.: Structure of concrete.

(c) Tarmac a matrix of gravel held in a matrix of tar, ideal for roads.
2.3.2.2 Fibre reinforcement composites
Brittle materials fail by cracks spreading through them with little resistance. Adding fibres
prevents the crack opening and spreading. Technologically, the most important composites are
those in which the dispersed phase is in the form of a fiber. Design goals of fiber-reinforced composites
often include high strength and/or stiffness on a weight basis. These characteristics are expressed in
terms of specific strength and specific modulus parameters, which correspond, respectively, to the
ratios of tensile strength to specific gravity and modulus of elasticity to specific gravity.
This method of reinforcement can range from the glass fibers used in GRP plastic moldings to the thick
steel rods used to reinforce concrete to improve its performance overall (tension in addition to
compression), metal reinforcing rods are added.
Consider a cylindrical rod made with fibers and a matrix material. Let the volume of the fibre be Vf and
the volume of the matrix be Vm. The volume of the resulting composite is Vc = Vf + Vm.
The mass of the fibre is: mf = f Vf
The mass of the matrix is: mm = m Vm
The mass of the composite is: mc = c Vc= f Vf + m Vm
c Vc= f Vf + m Vm = f Vf + m (Vc - Vm)
Examples are : Reinforced concrete; Glass reinforced plastics (GRP); Carbon fibers; Aramid fibers.

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(i) Reinforced concrete: Concrete itself is a particle-reinforced material. Concrete is very brittle and
weak in tension so it is normally only used for support type structures (columns and solid floors). By
adding steel rods, the structure becomes stronger in tension and withstands some bending.
Hence bridges, unsupported floors and other structures where some
bending occurs can be made to take the tension. The resulting
structure is lighter than steel on its own.
Not only the amount of reinforcement but also its positioning (the
tension side is the side of the beam that is on the outside of the
'bend' when the beam 'gives' under the effect of an externally applied
load) of is important.
Fig.: Simple reinforced concrete beam.
Glass and carbon fibers when made new are very strong and flexible and if they are imbedded in a
matrix of plastic (thermosetting) they retain their high tensile strength. The result is a very strong
flexible and light structure. Many things are made from these materials such as boat hulls, tennis
rackets, fishing poles and so on.
(ii) Glass- reinforced plastic (GRP): This important composite material is produced when a plastic
material, usually a polyester resin is reinforced with glass fibre in strand or mat form.
The resin is used to provide shape, color and finish, whilst the glass fibers, which are laid in all directions,
impart mechanical strength. When a GRP moulding is correctly 'laid up', the thick, viscous resin
completely surrounds and adheres to the glass fibers of the 'chopped strand mat' or the woven fibre
glass cloth. The resin sets to give a hard. Rigid structure. To shorten the setting time a catalyst
(accelerator) is often added to the resin immediately before moulding.
To improve the appearance of the 'rough side' of
the moulding (the side not in contact with the
polished surface of the mould), a surfacing tissue
is added made up from finer strands of mat. As
shown, Glass-reinforced plastic is widely used for
products that require high strength to weight
ratios such as boat hulls, car bodies, gliders, etc. It
has the advantages of being resistant to most
environments and it can be used to form more
complex shapes than is possible in wood or sheet
metal.
3. Carbon fibers
These have a higher elastic modulus and lower density than glass fibers, and can be used to reinforce
composite materials having a higher strength to weight ratio for a wide range of lightweight, highstrength applications. E.g. they are used in the manufactures of gas turbine fan blades, racing car body
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panels, high-performance tennis racket frames and high-performance golf club shafts.

2.3.3 STRUCTURAL COMPOSITES


A structural composite is normally composed of both homogeneous and composite materials, the
properties of which depend not only on the properties of the constituent materials but also on the
geometrical design of the various structural elements. Laminar composites and sandwich panels are two
of the most common structural composites.

2.3.3.1 A laminar composite is composed of two-dimensional sheets or panels that have a preferred
high-strength direction such as is found in wood and continuous and aligned fiber-reinforced plastics.
The layers are stacked and subsequently cemented together such that
the orientation of the high-strength direction varies with each
successive layer (E.g.: adjacent wood sheets in plywood are aligned
with the grain direction at right angles to each other). Laminations
may also be constructed using fabric material such as cotton, paper, or
woven glass fibers embedded in a plastic matrix. Thus a laminar
composite has relatively high strength in a number of directions in the
two-dimensional plane; however, the strength in any given direction
is, of course, lower than it would be if all the fibers were oriented in
that direction.
Fig.: The stacking of successively oriented, fiber-reinforced layers for a laminar composite.
Brittle materials such as concrete and ceramics are strong in compression but weak in tension since they
are susceptible to crack propagation.

Fig.: crack propagation in a non-reinforced ceramic material


The use of composite materials overcomes this problem by preventing the crack from 'running' through
use of lamination.

Fig.: Principles of behavior of a laminated composite when in tension


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Also the use of reinforcing fibers which hold the brittle matrix in compression, so an external tensile load
cannot open up any surface cracks and discontinuities

Fig.: Principles of reinforced composite materials for fibre reinforcement


Plywood: is a man-made composite that overcomes natural woods problem of steep directional
strength by exploiting its directivity of the strength. Wood like all materials reinforced by parallel fibers
has highly directional strength characteristics. Loading the plank in a plane perpendicular to the lay of
the grain exploits its greatest strength characteristics. Otherwise, (parallel loading to the lay of the
grain), it breaks easily since the lignin bone is relatively weak compared with the natural cellulose
reinforcement fibers.

Fig.: Effect of the direction of grain on the strength of wood.


This issue is thrashed out by building plywood from veneers (thin sheets of wood) bonded together by a
high-strength and water-resistant synthetic resin adhesive;
Wherein veneers are superposed in a
manner that the grain of each successive
layer is perpendicular (at right angles) to
the preceding layer. When the correct
number of veneers have been laid up, the
adhesive component of the composite is
cured under pressure in a hydraulic press.
Fig.: Structure of plywood.

2.3.3.2 A sandwich panel consists of two outer sheets, or faces, relatively stiff and strong (typically
aluminum alloys, fiber-reinforced plastics, titanium, steel, or plywood) that are separated by and
adhesively bonded to a thicker core. They are designed to be light-weight beams or panels as the outer
sheets impart high stiffness and strength to the structure and they must be thick enough to withstand
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tensile and compressive stresses.


The core material, typically: rigid polymeric foams (i.e.
phenolics, epoxy, polyurethanes), wood (i.e., balsa
wood), and honeycombs; is lightweight with low
modulus of elasticity. It provides continuous support for
the faces and must have sufficient shear strength to
withstand transverse shear stresses, and also be thick
enough to provide high shear stiffness so as to resist
buckling of the panel.
Fig.: Schematic diagram showing the cross section of a sandwich panel.
Popular core consists of a honeycomb structure used for roofs, floors, and walls of buildings; and, in
aerospace and aircraft for wings, fuselage, and tail plane skins. Thin foils are formed into interlocking
hexagonal cells (aluminum alloy or aramid polymer), with axes oriented perpendicular to the face planes

Fig:. Schematic diagram showing the construction of a honeycomb core sandwich panel.
Strength and stiffness of honeycomb structures depend on cell size, cell wall thickness, and the material
from which the honeycomb is made.

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3. METALLURGY AND METALLIC MATERIALS


Since the earliest days of the evolution of mankind, the main distinguishing features between human
beings and other mammals has been the ability to use and develop materials to satisfy our human
requirements. Nowadays we use many types of materials, fashioned in many different ways, to satisfy
our requirements for housing, heating, furniture, clothes, transportation, entertainment, medical care,
defense and all the other trappings of a modern, civilized society.
Most materials doesn't exist in its pure shape, it is always exist as a ores. During the present century the
scope of metallurgical science has expanded enormously, so that the subject can now be studied under
the following headings:
a) Physical metallurgy
b) Extraction metallurgy
c) Process metallurgy
In the recent years studying the metallurgy science gave to humanity an ever growing range of useful
alloys. Whilst many of these alloys are put to purposes of destruction, we must not forget that others
have contributed to the material progress of mankind and to his domestic comfort.
This understanding of the materials resources and nature enable the engineers to select the most
appropriate materials and to use them with greatest efficiency in minimum quantities whilst causing
minimum pollution in their extraction, refinement and manufacture.

3.1 PRODUCTION OF METALS


The common metals, excepting copper, do not occur free in nature, but are produced from their ores
which generally require chemical treatment at high heat in furnaces.
An ore is a natural substance composed of a metal chemically combined with one or more non-metallic
substances. Ores of different metals are sometimes found incorporated in the same mass, and almost all
ores are found mixed with impurities of a non-metallic nature, as rock, sand, clay, etc., known in mining
as gangue.
3.1.1 Extraction of iron ore: 4.6% of the earths crust is iron.
Crust
Mantle
Core
= 12800km
Fig.3.1: the earths parts
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4 types of ores are found in the earths crust:


(i) Black ore: known as Magnetite. Its chemical formula is Fe3O4 and its iron content is estimated
between 62 to 72%.
(ii) Red ore: Also called Hematite. Its chemical formula is Fe2O3 and its iron content is estimated
between 60 to 70%.
(iii) Brown ore: it is a product of the transformation of the Red ore. It is called Limonite and has a
chemical formula of 2Fe2O3.3H2O with iron percentage of 42 60%.
(iv) Carbonate: Also called Siderite or spathic iron ore. Its chemical formula is FeCO3 and its iron content
is 48%.
(V) Pyrite: it is a surphide of iron. It has a chemical formula of FeS2 and a proportion of 40-47% Fe.
3.3.2 Elimination of Gangue: This may be done more or less successfully with some ores by simple handpicking methods, while other ores must be crushed in a stone breaker or stamp mill, and the gangue
eliminated by dressing (passing running water over the mass in a succession of boxes ,the lighter
particles are removed to lower boxes). Some ores are subjected to weathering (they are heaped in the
open air and left exposed to sun and rain for weeks or months); this disintegrates the lumps and washes
away soluble salts and much powdered gangue.
5.3.3 Calcination: it consists of heating the ores to a point short of fusion. This drives away moisture and
some combined sulphur, and breaks up carbonates, changing them to oxides by driving off CO2.
Calcination is done crudely by making alternate layers of fuel and ore on the ground and lighting the
fuel, but more effective methods are to confine the ore and fuel by walls, or still better by kilns, in which
the heat is more intense and more uniformly distributed. After calcinating, the ore is ready for
transportation to the smelter.
5.3.4 Breaking up the Ore Compound
The actual metallurgical operation of breaking up the ore is done by heat in furnaces and is called the
dry process; or is done by making a solution of the metallic compounds and breaking up these by
chemical re-agents, known as the wet process or leaching. Smelting, as used in the dry process, is the
operation of fusing ores by heat in suitable furnaces.
Reduction is the separation of a metal from its oxide, though usually applied to the separation of a metal
from any ore, whether oxide or not. Roasting is the heating with free access of air in order to change the
ore partly or entirely to an oxide for reduction later on.
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The objective of each step in the processes of extracting a metal from its ores is to simplify the ore
compound. This is done, as has been outlined, by (1) separating the ore from the gangue, (2) driving
away certain ingredients by a heat short of fusion, and (3) fusing the ore one or more times in the
presence of certain re-agents called fluxes which combine with the non-metallic substances and allow
the liberated metal to separate and settle in an impure state. A metal thus obtained in the impure state
must be refined before it is used.
3.4.1 Smelting furnaces
They are built of common silica brick for the outer layers, and high grade refractory brick for the inner
layers. There are several modifications of furnaces for smelting ores of different metals, but all smelting
furnaces are included in the two general types of this class, namely, the blast furnace and the
reverberatory furnace. The main point of difference from the reverberatory furnace is that ore and fuel
are mixed in the blast furnace and are kept separate in reverberatory furnace.

Fig.: Reverberatory Furnaces for Roasting and for Melting


In a roasting furnace ores are roasted to simplify them before they are placed in the melting furnace.
The melting furnace is much used for smelting copper and tin ores, for refining copper and tin, and for
melting copper and brass in large quantities in the foundry for castings.
Both furnaces have several similar parts, as follows: G. Grate for fuel; D. Fuel door; A. Ash pit; W. Bridge
wall to separate the fuel from the ore or metal in the furnace; B. Furnace arch, which reflects heat down
upon the furnace charge; F. Hearth, on which the charge rests; C. Chimney opening, controlled by a
damper.
These furnace roofs are arched from side to side, and the sides are braced by iron plates connected with
long rods over and under the brickwork of the furnace. The melting furnace must generate a more
intense heat than the other; hence its fire box is larger. These furnaces have no air blast, and their draft
is produced by a tall chimney. The fuel is usually oil, gas, or soft coal which produces a long flame.
3.4.1.1 Blast furnace: so called because combustion is maintained by forcing a blast of air through the
mass of fuel, ore and flux which completely fills the furnace.
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Iron ore (100t)

Coke (50t)

Limestone (25t)

BLAST FURNACE
Blast furnace gas

Slag (30t)

Pig iron (54t)

Fig.3.2: Blast furnace charge and product

Fig.3.3: Main charge and chemical reaction in a blast furnace


Glossary:

Iron-bearing materials - The iron-bearing materials are usually iron ore, steelmaking slag, scrap.

Coke - The coke is added to provide the main chemical reagents (carbon and carbon monoxide)
for the iron ore reduction.
Flux - The flux, limestone and/or dolomite, is added to combine with ash in the coke and gangue
in the ores, to produce a slag that rises to the top of the pool of molten pig iron that collects in
the crucible.

Air supplies the oxygen for combustion of the coke as well as promoting the chemical reduction of the
iron oxide.
Specific chemical reactions in the blast furnace:
(1) Production of the reducing gas
(
(
93

(
)

)
(

(
)

)
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(2) Reduction of the iron oxide


(
Concurrent with the preceding of

)
(

The parts of this furnace are designated as follows, viz.: S: Shaft. This extends from the top down to the
part of largest diameter. B: Boshes. This is the tapered portion below the shaft. Water is circulated
through each bosh plate, by a system of external piping, to allay the intense heat at that part of the
furnace and thus prevent injury to the bosh walls. Y: Tuyere holes. These openings conduct into the
furnace the air of the blast. They are metal tubes surrounded by a helix of pipe through which water
circulates to keep the end of the tuyere from melting in the furnace.
M: Hot blast main. This is a pipe, made of iron plates and
lined inside with refractory brick. It encircles the furnace,
delivering highly heated air from the blast stove to the
tuyeres. H. Hearth. This is the part of the furnace below the
line of tuyere holes which receives molten slag and metal,
and when the slag, which floats on the metal, reaches the
height of the cinder notch C, it is drawn off. T. Tapping
hole. Metal is taped from the hearth through this hole. In
tapping, an iron bar is used to dig out the clay plug stopping
the hole, and when the metal has run out, another plug is
forced in to stop the hole. G: Gas main or "down comer," a
brick-lined pipe leading away the gaseous products of the
blast and delivering them, through the dust catcher, to the
gas main, Q, which distributes them to the blast stoves. J:
Shaft lining. This lining is of highest quality refractory brick
(fireclay). D: Silica brick body. The furnace body is encased
in plate steel marked D. K: Cone. This is a cone-shaped
hollow cast iron ring built into the top or "throat" of the
furnace.
Fig.3.4: Main parts of a blast furnace
L: Bell, a cast iron cone suspended by a heavy chain from the lever N. This cone closes the throat of the
furnace and is opened for admitting materials of the furnace charge. R: Stand pipe. Before lowering the
bell to admit a new charge to the furnace, the lid of the stand pipe is raised to relieve the gas pressure at
the top of the furnace. This obviates the escape of gas and flame from the furnace throat.
The refractory materials commonly used in all branches of smelting, refining and melting of metals,
including the processes of steel making, and in heating furnaces, are: Silica (common sand), SiO2; Silicate
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of Aluminum (clay), Al2O3.2SiO2.2H2O; Magnesite (magnesia), MgO; Chromite (chromium oxide),


Cr2O3FeO; Dolomite (magnesian limestone); Bauxite (alumina), Al2O3.
Pig iron produced from the BF is not the end product; it is still impure; in that it is high in carbon content
and not suitable for making engineering materials since it would be extremely brittle and weak. Then, it
must undergo some refining treatments to become useful.
Direct reduction process may replace the blast furnace iron ore; coal and oxygen (from lance) are
reacted in a single smelting vessel. Steel rather than iron can be the product of the process, and it can go
directly to ladles for pouring into ingots or into continuous caster.
3.4.1.2 Refining processes
In pig iron, c =4 or 5%; in addition to the carbon, it contains: Silicon, sulfur, phosphor, manganese as well
as physical inclusions of non metallic materials from the ore. Thus a number of impurities besides
carbon must also be removed.
In the blast furnace, carbon in form of coke was used to remove oxygen: combination of O and C to form
CO. Now, oxygen in the form of air (O2) or pure oxygen from CO, once again must be used to remove the
carbon in iron.
The oxygen and additional fluxing ingredients, reduces the level of other impurities in the pig iron.
The early Bessemer furnace used in purification of pig iron to steel employed a sustained blast of air in
the molten iron thats why is phased out. Today, the purification of pig iron into steel is accomplished in
three processes:
Basic oxygen furnace: the charge is 25% scrap and 75% molten pig iron. Oxygen lances are lowered into
the melt and blowing is initiated. Large amount of pressurized oxygen are introduced into the molten
charge. The heat of this reaction provides the heat for the process. When the charge is, sufficiently
blown (the carbon content is reduced to desired level); the oxygen lances are withdrawn.
Open health furnace (burning fuel-air mixture over the pool of metal)
Electric furnace (electric arc between carbon electrodes lowered in the proximity to the charge which is
many time the scrap)

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Fig. 5.5: Three types of furnaces used in pig iron purification

3.2 ALLOY SYSTEMS AND PHASE DIAGRAMS


A system is any portion of the material universe which can be isolated for consideration of the changes
that may occur within it under varying conditions. Its components are the different elements or
chemical compounds. Due to number of components, there are Unary, binary or tertiary phase
diagrams.
A system composed of one phase is described as Homogeneous, whereas that of 2 or more phases is
termed Heterogeneous system.
Variance or degree of freedom is the number of intensive variables, such as temperature, pressure and
concentration of the components which must be arbitrary fixed in order that the condition of the
system must be perfectly defined. Then it is said to be Mono, bivariant or invariant (1, 2, 0 degree of
freedom).

3.2.1 ALLOY SYSTEMS


Alloy is a metal composed of a mixture of elements. Most of alloys are composed of a base metal with
small amounts of additives or alloying elements. The typical examples of alloys are steel/cast iron (iron
base alloys), bronze/brass (copper base alloys), aluminum alloys, nickel base alloys, magnesium base
alloys, titanium alloys.
An alloy can be either homogeneous or a mixture. If homogeneous, it can only be a solid solution or
compound. If a mixture, it is a combination of phases or a mixture of 2 pure metals or a mixture of 2
solid solutions.
When 2 liquid substances are mixed, they may dissolve in one another in all proportions, forming a
homogeneous liquid solution, or they may be insoluble in one another, either partially or totally, and
separate into 2 liquid layers on density grounds like oil and water.
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Although 2 substances may be completely soluble in one another in the molten state, it does not
necessarily mean that the liquid solution solidify to give a homogeneous solid phase or solid solution.
They may be: totally insoluble or totally soluble in one another when solid is partially soluble in one
another when solid or combine with one another to form a compound.
3.2.1.1 SOLID SOLUTIONS
Most metals are completely and mutually soluble (they are miscible) in the liquid state, that is when
they are molten. Some such as copper and nickel, not only form solutions in the molten or liquid state
but remain in solution upon cooling and solidifying to become solid solutions. Solid solution is a phase,
where two or more elements are completely soluble in each other. Solid solution formation usually
causes increase of electrical resistance and mechanical strength and decrease of plasticity of the alloy.
Depending on the ratio of the solvent (matrix) metal atom size and solute element atom size, two types
of solid solutions may be formed:
3.2.1.1.1 Substitutional solid solution (unlimited solubility): If the atoms of the solvent metal and solute
element are of similar sizes (not more, than 15% difference), Atoms of the solute can substitute atoms
of the solvent without causing any changes to the lattice structure.
According to Hume-Rothery laws, the factors leading to its formation are as follows:
- Atomic size: Atoms of the solvent and solute must be approximately of the same size (not differ more
than 15%).
- Electrochemical series: there is only a small difference in charge between alloying components (their
charges not very dissimilar). They have nearly the same electro-negativity otherwise they will form
compounds.
- The elements must have the same type of crystal lattice structure
- No relative difference in valence, valence electrons difference promotes the formation of compounds.

(a)

(b)

(c)

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Fig.4.1: Substitutional solid solution: (a) FCC crystal of copper (b) FCC crystal of Nickel (c)
Substitutional solid solution of Cu and Ni.

3.2.1.1.1 Interstitial solid solution (Limited solubility): If the atoms of the alloying elements are
considerably smaller, than the atoms of the matrix metal, interstitial solid solution forms, where the
matrix solute atoms are located in the spaces between large solvent atoms. Thus, it is formed when
atoms of small radii fit into the spaces or interstices of the lattice structures of larger solvent atoms
(>1A). e.g: H, B, C, N and O. The lattice tends to expand when an interstitial solid solution is formed. E.g:
Carbon in the iron limited to just about 2% at 11300C, the fact that these atoms occupy interstitial
positions, restricts slip movements of atom planes.
Carbon
interstitial
atom in
BCC

Fig.4.2: Interstitial solid solution


When the solubility of a solute element in interstitial solution is exceeded, a phase of intermediate
compound forms. These compounds (WC, Fe3C etc.) play important role in strengthening steels and
other alloys.
Some substitution solid solutions may form ordered phase where ratio between concentration of matrix
atoms and concentration of alloying atoms is close to simple numbers like AuCu3 and AuCu.
The properties of alloys formed are different from those of the pure metal: Increase in hardness, yield
strength and ultimate tensile strength, Decrease in ductility, Reduced electrical conductivity, Better
mechanical properties at elevated temperatures (e.g.: creep strength).
There are many types of alloying systems which they are:
- Binary system: It means that alloying have two metals only.
- Ternary system: It means that alloying have three metals only.
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- Multi system: It means that alloying have three and more than those metals.
Upon cooling into the solid state, binary alloys can be classified into the following types.
Simple eutectic type: The two components are soluble in each other in the liquid state but are
completely insoluble in each other in the solid state.
Solid solution type: The two components are completely soluble in each other both in the liquid
state and in the solid state.
Combination type: combines some of the characteristics of both the previous types. The two
components are completely soluble in the liquid state, but are only partially soluble in each other in
the solid state.
We are going to consider these three types of binary alloy systems and their phase equilibrium diagrams

3.2.2 PHASE DIAGRAMS


A pure substance may exist in 3 states: solid, liquid and vapor; each of these states being a single phase.
Phase diagrams (PD), also known as equilibrium diagrams or constitutional diagrams are a very
important tool in the study of alloys. An alloy is defined as the substance that composed of two or more
chemical elements such that the metallic atoms predominate in composition and the metallic bond
predominates.
A phase diagram is a graphical representation of the phases present in any alloy system at different
temperatures and compositions of the components i.e. graphic relationship between temperature and
weight ratios of elements and alloys contribute to the built of the diagram. It shows the temperature at
which a solid alloy begins and finishes melting and the possible phase changes which will occur as a
result of altering the composition or temperature.
Where Phase is a uniform part of an alloy, having a certain chemical composition and structure, and
which is separated from other alloy constituents by a phase boundary. For example the salt water
solution have a four possible phases: Water vapor (steam), Liquid salt solution (sodium chloride in
water), Crystals of water (ice) and Crystals of salt (sodium chloride).
Phase diagram has temperature as its ordinate and composition (alloy) as abscissa, which gives the
relationship between the composition, temperature and structure of an alloy in series.
In general, the understanding of the phase diagrams for alloy system is extremely important because
there is a strong correlation between microstructure and properties, and the development of
microstructure of an alloy is related to the characteristics of its phase diagram.
The relationship between states or phases, for various conditions of temperature and pressure can be
shown on a simple diagram.

3.2.2.1 Phase diagram classification

Based on number of components (materials) meting elements: unary,. Binary, ternary

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Fig.: The approximated carbon unary system


0

Solution

10
0
0

Nacl + Sol
Nacl.2H2O + Sol

Ice + Sol
Ice + Nacl.2H2O

-20
10

30

40

% Nacl

Fig.: unary P/T phase diagram for Water and binary phase diagram H2O Nacl
Applying Gibbs phase rule: P + F = C +2, P: number of phases (ie, solid, liquid, or gas); C: number of
components; F: Degree of freedom
Water:
a) At the triple point: P = 3 (solid, liquid, and gas); C= 1 (water); P + F = C + 2. F = 0 (no degree of freedom)
b) liquid-solid curve: P = 2, 2+F = 1 + 2, F= 1; One variable (T or P) can be changed
c) Liquid, P =1, So F =2
Two variables (T and P) can be varied independently, and the system will remain a single phase
Further the equilibrium conditions are obtained to draw the PD by extremely slow heating and cooling
so that if a phase change is to occur, sufficient time is allowed.
Below classification is according to the relation of the components in the liquid and solid states
1. Components completely soluble in the liquid state
completely soluble in the solid state
Insoluble in the solid state: the eutectic reaction
Partly soluble in the solid state: the eutectic reaction
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2.
3.
4.

Formation of a congruent-melting intermediate phase


The peritectic reaction
components partly soluble in the liquid state: the monotectic reaction
Components insoluble in the liquid state and insoluble in the solid state
Transformations in the solid state
Allotropic change
Order-disorder
The eutectoid reaction
The peritectoid reaction

Interpretation of phase diagrams


The rules necessary to interpret the phase diagrams are,
1. Present phases
2. The chemical composition of each phase
3. The lever rule (the amount of each phase)
Rule 1: prediction of phases
Phase can be predicted only when temp and composition is known, thus a vertical line drawn (on the
phase diagram constructed for bismuth and antimony and shown in fig. 4) for 30% bismuth and the
temp selected as 1200, 900 and 6000F respectively noted as point 1, 2 and 3.
At point 1 only one phase as liquid and at point 2 two phases that are liquid and solid followed by at
point 3 only one phase as solid. Similar analysis can be made for any other alloy compositions and temp
in the phase diagram
Rule 2: Phase composition
To find out the composition of phases which are stable at a give temp (say 9000F in figure 4 draw a
horizontal line (isothermal line), OP at given temperature.
Liquid phase (p) has the compositions roughly 62% bismuth and solid phase (O) has the composition of
roughly 14% bismuth, of course, the reminder is antimony in both cases.
Rule 3: Lever arm principle: It is interesting to note that the composition of both liquid and solids in the
two-phase mixture (between liquidus and solidus lines) is continuously changing. Hence, It is clear that
the liquid remains in the 2 phase mixture contains less Ni and more Cu than solid solution that has
begun to form at any temperature during this range: Nickel has a higher melt point than Cu, hence its
solidification from liquid solution takes place before Cu.
Fraction of the solid phase = (Wo Wl)/(Ws-Wl)

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First solid
T1
Tie line

T2

Last liquid
CL

Cs

Fig.: Lever rule for an alloy with C percentage composition.


We note further that the solid solution that in forming gets continuously richer in Cu. AB: amount of
solid solution (C CL), BC: amount of liquid (Cs C). The % proportion of the solid solution ps = (Length
of segment AB/ Length of tie line AC) X 100%. = (C - CL)/ (Cs - CL) X 100%
Gibbs phase rule:
The phase rule establishes the relationship between the number of degrees of freedom (F), the number
of components (C) and the number of phases (P), mathematically expressed as follows:
Where P is the number of phases (e.g., solid liquid etc), F is the number of degrees of freedom or the
number of physical variables (pressure, temperature and concentration) that can be independently
changed without altering the equilibrium and C is the number of components in the system, for instance
Cu and Ni are the components of Cu-Ni phase diagram.
In metallurgical systems, where pressure is fixed at one atmosphere and the only variable is
temperature, thus actual phase rule is simplified to the following form;
Since the degrees of freedom F cannot be less than zero,
or
, which means the
number of phases (P) in a system cannot exceed the number of components Plus one.
The phase rule becomes particularly useful when dealing with multi-component systems to determine
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whether the microstructures are in equilibrium or not.


Example: Determine the relative amount of two phases of an alloy of 30%Bi and 70%Sb And determine
the number of degrees of freedom using the phase rule?

Fig. : Interpretation of phase diagram


(1) To determine the relative amount of two phases,
Draw a vertical line, AL (in this case, consider the line drawn at 30%Bi) on the composition scale,
which gives the total or overall composition of the alloy (like 30Bi-70Sb)
The intersection of this composition vertical line AL on a isothermal line OP is the fulcrum (noted as
point M) of a simple lever system, whereas OM and OP are two lever arms. The isotherm line OMP
is called as a tie line, since it joins the composition of two phases in equilibrium at a specific
temperature.
The relative lengths of the lever arms multiplied by the amounts of the phase present must balance,
which is called lever rule, since the amount of given phase multiplied by its lever arm is equal to the
amount of the other phase multiplied by its respective lever arm.
The lever rule expressed in mathematical form to determine the relative phases:
(a) The amount of solid phase =
(b) the amount of liquid phase =

(
(
(
(

)
)
)
)

= 66.67%
= 33.33%

(2) Consider, the points X and Y, to determine the number of degrees of freedom using the phase rule.
Point X, in the region above the liquidus, Number of components, C = 2, since it is a binary system
of Bi and Sb, number of phases, P = 1 (liquid), applying the rule, F=C+2-P = 2+2-1 = 3 degrees of
freedom
2. Point Y, between the liquidus and solidus, C=2, P = 2, applying rule, F=C+2-P = 2+2-2 = 2 degrees
of freedom.
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4.3.1 SYSTEMS OF BINARY EQUILIBRIUM PHASE DIAGRAMS (or a 2-component system)


There are 3 variables: Temperature, pressure and composition. Then, the representation would require
a 3 dimensional model. But in most cases, phase relationships are determined at constant pressure
thereby, it is possible to represent the relationships in a 2 dimensional graph. There are 3 basic types of
binary phase diagrams:
4.3.1.1 Complete solubility in the solid state (isomorphism): An isomorphous system is one in which
there is complete intersolubility between the two components in the vapor, liquid and solid phases.
Elements A and B completely soluble in each other in both liquid and solid state. Depending on the ratio
of the solvent (matrix) metal atom size and solute element atom size, two types of solid solutions may
be formed: substitution or interstitial.

Fig.: Complete solubility of Cu and Ni; Plotting equilibrium diagrams from cooling curves for Cu-Ni
solid solution alloys. Cooling curves and equilibrium diagram.
The Cu-Ni system is both a classical and a practical example since the monels, which enjoy extensive
commercial use, are Cu-Ni alloys. Many practical materials systems are isomorphous.
This system is composed of 3 distinct phase areas separated by transformation lines (i) Liquid, (ii) liquid
and solid solution and (iii) solid solution. Consider a solidification of an alloy with 40% Ni: (1) above the
liquidus line, the two metals go into a liquid solution Ni and Cu atoms are homogeneously distributed in
this liquid solution. When the alloy is cooled to just below the liquidus temperature, some tiny solids
and solid solution begin to form in the liquid solution (2). Further drop of temperature leads to
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formation of more solids and growth of the crystals until only very little liquid remains (3) and (4). As the
alloy cools below the solidus temperature, any remaining liquid is solidified to solid solution (5).

Equilibrium cooling and/or heating of solid solution alloy, with its development of microstructure:
Lets consider the very slow cooling, under equilibrium conditions of a particularly 70A-30B to observe
the phase change that occur
This alloy at temp T0 is a homogeneous single-phase liquid solution (fig a) and remained so until
temp T1 is reached. Since T1 is on the liquidus line, freezing or solidification now begins. The first
nuclei of solid solution to form, 1, will be very rich in the higher melting point metal A and will be
composed 10 of 95A-5B (rule 1 and 2), just after the start of solidification, the composition of the
liquid is 69A-31B (fig b)

Fig.: The slow cooling of &0A-30B alloy with microstructure at various points of solidification
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Still lowering the temp up to T2, the liquid composition is at L2


and the solid solution forming at T2 is 2. Applying rule 1 and 2,
2 is composed of 10B. It is therefore, as the temp decreases B
becomes richer in solid as well in liquid solution. At T2, crystals
of2, are formed surrounding the 1 composition cores and
also separate dendrites of2 (fig. 6).
Then at T3, the solid solution will make up approximately threefourths of all material present. At this temp (fig. 5 d) the
composition of liquid is 42A-58B and that of solid is 80A-20B.
Fig.: Schematic view of the alloy 30B at temp T2 before diffusion
Applying the lever rule (rule 3) at T3, the relative quantities of _3 and L3 is found to be 73.7% and 26.3%
respectively
Finally, the solidus line, where the temp is noted as T4, the last liquid L4, very rich in B, solidifies
primarily at the grain boundaries (fig 5e). However, diffusion takes place on further lowering the
temp, at T5, all the solid solution will be of uniform composition (70A-30B), which is the overall
composition of the alloy (fig f)
The microstructure of a slow-cooled
solid solution alloy shown in figure
below, observed to be only grains
and grain boundaries. There is no
evidence of any difference in
chemical composition inside the
grains, exhibits that the diffusion
has made the grain homogenous.
Fig.: Microstructure of a solid solution iron alloy at a magnification of 100X

4.3.1.2 Complete insolubility in the solid state (Eutectic type): Although metals A & B are mutually
soluble in the liquid state, both components retain their individual identities of crystals of A and crystals
of B in the solid state, i.e. when a liquid solution of fixed composition, solidifies at a constant
temperature, forms a mixture of two or more solid phases. This process is reversible, the reaction is
expressed as:

Eutectic system refers to a specific alloy composition that freezes at a lower temperature than any other
composition. The eutectic temp and composition determine a point on the phase diagram, where a
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liquid solidifies into two different solid simultaneously called as eutectic point.

Fig. : Cooling curves for for a series of two metals insoluble in solid state
The line joining the points where solidification begins is referred to as the liquidus and that the line
joining the points where solidification is complete is referred to as the solidus.
This type of equilibrium diagram gets its name from the fact that at one particular composition (E), the
temperature at which solidification commences is a minimum for the alloying elements present. With
this composition the liquidus and the solidus coincide at the same temperature, thus the liquid changes
into a solid with both A crystals and B crystals forming instantaneously at the same temperature. This
point on the diagram is called the eutectic, the temperature at which it occurs is the eutectic
temperature, and the composition is the eutectic composition. The eutectic composition is a unique alloy
that gives the lowest melting point in the system and its cooling curve looks like that of the pure metal.
Alloy C is a mixture of pure metal A and the eutectic mixture, and its cooling curve in the liquid-solid
phase zone is similar to that of a solid solution.
Alloy C, at the liquidus solids rich in metal A are crystallized. When the eutectic temperature T E is
reached, a eutectic reaction takes place, where all the remaining liquid is transformed in a solid solution
of composition E. The eutectic alloy E is a duplex structure containing crystals of A and B side by side. It
crystallizes without going through two phase stage that would otherwise delay the crystallization (it is
often used in solders and fuses).
Many casting alloys are eutectic alloys as the liquid can be melted and poured into a mould at low
temperature; this minimizes heat required for melting and the products have less casting defect such as
gas porosity. Cast iron and most cast aluminum alloys are eutectics.
However sometimes eutectics are brittle and may affect the overall alloys ductility. Brittle failure during
cold working of alloys, that results from the fracture of the eutectic phase in grain boundaries is called
Cold shortness. In some cases, they result into material failure during forging, as the eutectics may
melt far below the forging temperature. This type of failure is called hot shortness.

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This figure shows how by joining a1b1,


a2b2,.. points, the equilibrium diagram
for a such a system can be obtained.
consider the cooling and solidification of
three compositions such as 1, 2 and 3 as
shown in next figure: As the temp falls to
T1, crystal nuclei of pure Cd begin to form.
Since pure Cd is deposited, it follows that
the liquid becomes richer in Bi; on further
decreasing temp to T2, the composition
moves on to left 3
and at T2 more Cd is deposited and dendrites begin to develop from the already formed nuclei (fig.d
below).

Fig.: The Bi-Cd equilibrium diagram


On one hand, the growth of Cd dendrites and the other hand consequent enrichment of the remaining
liquid in Bi, continues until the temp has fallen to 1400C, the eutectic temp in this case. The remaining
liquid then contains 40%Cd and 60%Bi, the eutectic composition.
Point (1) 20%Cd and 80%Bi: Contrary to point 3, in this case crystal of pure Bi form first, enriching the
melt with Cd. The composition of the melt or liquid moves to right until ultimately the point E is reached
and the remaining liquid solidifies as eutectic.
Point (2) 40%Cd and 60%Bi: No solidification occurs until the melt reaches the eutectic temp, 1400C, the
two pure metals crystallize together to give a characteristically fine aggregate known as eutectic (fig c)
Eutectic Microstructures: There are a number of different morphologies for the two phases in a binary
eutectic alloy. Morphology means the form, shape or outward microstructure of a phase. Of prime
importance is the minimization of the interfacial area between the phases. The rate of cooling can also
have an important effect.
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Fig.: (a) lamellar, (b) rodlike, (c) globular, and (d) acicular (or needlelike).
Congruent melting intermediate phase (Equilibrium diagrams with intermediate compounds):
Two components may also form an intermediate compound at certain composition. When one
phase changes into another phase isothermally (i.e., at constant temp) and without any change in
chemical composition, it is said to be congruent phase change or congruent transformation. The

melting point of such an intermediate compound or compounds may be above, below or


between the melting points of the pure components.
Any intermediate phase may be treated as another
component on a phase diagram. If this phase has a narrow
range of composition, it is then represented on the diagram
as a vertical line and labeled with a chemical formula of the
compound which is indicated as AmBn, where m and n are the
number of atoms combined in the compound. For example,
magnesium and tin form an intermediate phase which has the
chemical formula Mg2Sn. In this case, Mg is equivalent to A; 2
is equivalent to m; Sn, is equivalent to B and n is equal to 1.
Fig. : Composition and melting point of pure A, pure B and a compound AmBn
These compounds have a different crystalline structure from that of the parent substances and
consequently form another solid phase in the system. The following figure illustrates such a system in
which the intermediate compound is formed from two components, A and B. Such a binary compound
AB forms reversibly as the result of phase reactions between two components and exhibits a
composition constant and independent of pressure and temperature. The diagram also indicates that
there are now two eutectic points, E and E, formed between the compound AB and solid A and the
compound AB and solid B.

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The compound has a congruent melting point, giving a


liquid of the same composition as the crystal, and it does
not form solid solutions with either component A or B.
The systems A-AB and AB-B may be considered as two
separate systems within the boundary system A-B, and
they will behave similarly, as exemplified by copper-zinc
alloys, in which the maximum solubility has been reached
and above which the components form intermetallic
compounds. C is the melting point (maximum) of the
compound AB having the composition C. E is the eutectic
of solid A and solid AB. E is the eutectic of solid AB and
solid B.

Fig.: Binary system showing an intermediate compound.


4.3.1.3 Systems with partial solubility in the solid state (Combination type): Many metals and
non-metals are neither completely soluble in each other in the solid state nor are they completely
insoluble. It occurs in alloys where atoms of one of the components are able to occupy interstitial
positions. Due to limited number of interstices, only a limited number of the dissolving atoms can be
accommodated. In this system there are two solid solutions labeled and . The use of the Greek letters
, , , etc., in phase equilibrium diagrams may be defined, in general, as follows:
A solid solution of one component A in an excess of another component B, such that A is the solute
and B is the solvent, is referred to as solid solution .
A solid solution of the component B in an excess of the component A, so that B now becomes the
solute and A becomes the solvent, is referred to as solid solution .
In a more complex alloy, any further solid solutions or intermetallic compounds which may be
formed would be referred to by the subsequent letters of the Greek alphabet. That is, , , etc.
The solid solution is rich in lead while is rich in tin.

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Consider a 25% Sn, 75% Pb alloy at 230C as drawn below. Continuing with the same alloy at the same
temperature; Finding Relative Amounts (proportions of the phases): To find the weight percent of a
phase, use the tie line as a lever with fulcrum at the point of interest and lever ends at the phase
compositions.
Alloys that contain 0-2%Sn solidify to form a single phase solid solution and remain so even after the
alloy has cooled to room temperature. Alloys containing between 2 and 19%Sn also solidify to produce a
single solution .
To determine the relative amounts of the two phases, erect an ordinate at a point on the composition
scale which gives the total or overall composition of the alloy. The intersection of this composition
vertical and a given isothermal line is the fulcrum of a simple lever system. The relative lengths of the
lever arms multiplied by the amounts of the phase present must balance. As an illustration, consider
alloy I in fig. The composition vertical is erected at alloy I with a composition of e% of B and (100e)% of
A. This composition vertical intersects the temperature horizontal (Te) at point e. The length of the line
feg indicates the total amount of the two phases present. The length of line eg indicates the
amount of solid.

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10

15

opposite leg 15

(100%) 60%
total length
25

15%

25%

40% %L opposite leg 10 (100%) 40%


total length
25

Example of eutectic composition:


(a) Composition of the phases:
Alpha: 19.2% Sn; Liquid: 61.9% Sn
Amount of phases:
51% of alpha phase: (61.9-40)/(61.919.2); 49% of liquid phase
(b) Phases: alpha and beta;
Composition of the phases: Alpha:
19.2% Sn; Beta: 97.5% Sn
Amount of phases:
45.5% of alpha:
(97.5-61.9)/(97.5-19.2)
54.5% of beta phase
Fig. Eutectic composition for alloys 40% and 61%Sn
However as the alloy cools to below the solvus line, a solid state reaction occurs, permitting a second
solid phase to precipitate from the original phase Dispersion or precipitation hardening.
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Fig.: (a) Lead Tin (Pb & Sn) phase diagram, (b) Its microstructure

Eutectic reaction: L +

Peritectic reaction: + L

+L
L

Monotectic reaction: L1 L2 +

L1

L2

+ L2

Eutectoid reaction: +
Peritectoid reaction: +

+
+

Fig.: The five three phase reactions in binary systems.


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Eutectic reaction: when a liquid solution of fixed composition, reversibly solidifies at a constant
temperature, forms a mixture of two or more solid phases

Peritectic Reaction: A liquid and solid react isothermally to form a new solid on cooling, the reaction
expressed in general as;

Eutectoid Reaction: A solid phase transforms on cooling into two new solid phases

Peritectoid reaction: The two different solid phase on cooling transforms into a new solid phase,

Transformations in the solid state (Allotropy):


Several metals may exist in more than one type of crystal structure depending upon the temperature.
Iron, tin, manganese and cobalt are the examples of metals which exhibit this property known as
allotropy. Figure below shows a cooling curve for pure iron with allotropic forms of iron marked over it.
Iron is molten above 15390C. it solidifies in the B.C.C (delta)
On further cooling at 14000C, a phase change occurs and the atoms rearrange themselves into the _
(gamma) form which is FCC and non-magnetic. On still further cooling at 9100C, another phase change
occurs from FCC non-magnetic -iron to BCC non-magnetic (alpha) iron. Finally at 7680C, the iron (BCC)
becomes magnetic without a change in lattice structure. The following phases are involved in the
transformation, occurring with iron-carbon alloys:
L Liquid; -iron (BCC structure, Paramagnetic); -iron also named as Austenite (FCC structure, Ductile,
Non-magnetic); -iron also named as Ferrite (Bcc structure, fairly ductile, Ferromagnetic); Fe3C also
named as Cementite (Orthorhombic, Hard, Brittle).
Critical temperatures:
Upper critical temperature (point) A3 is the temperature, below which ferrite starts to form as a result of
ejection from austenite in the hypoeutectoid alloys.
Upper critical temperature (point) ACM is the temperature, below which cementite starts to form as a
result of ejection from austenite in the hypereutectoid alloys.
Lower critical temperature (point) A1 is the temperature of the austenite-to-pearlite eutectoid
transformation. Below this temperature austenite does not exist.
Magnetic transformation temperature A2 is the temperature below which a-ferrite is ferromagnetic
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Figure.: Iron-carbon phase diagram.


Phase compositions of the iron-carbon alloys at room temperature:
Hypoeutectoid steels (carbon content from 0 to 0.83%) consist of primary (proeutectoid) ferrite
(according to the curve A3) and pearlite.
Eutectoid steel (carbon content 0.83%) entirely consists of pearlite.
Hypereutectoid steels (carbon content from 0,83 to 2.06%) consist of primary (proeutectoid) cementite
(according to the curve ACM) and pearlite.
Cast irons (carbon content from 2.06% to 4.3%) consist of proeutectoid cementite CT ejected from
austenite according to the curve ACM , pearlite and transformed ledeburite (ledeburite in which
austenite transformed to pearlite).

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Invariant Reactions:

Max. Solubility of C in ferrite=0.022%; Max. Solubility of C in austenite =2.11%


The following phase transformations occur with iron-carbon alloys:
Alloys, containing up to 0.51% of carbon, start solidification with formation of crystals of -ferrite.
Carbon content in -ferrite increases up to 0.09% in course solidification, and at (1493C) remaining
liquid phase and -ferrite perform peritectic transformation, resulting in formation of austenite.
Alloys, containing carbon more than 0.51%, but less than 2.06%, form primary austenite crystals in the
beginning of solidification and when the temperature reaches the curve ACM primary cementite stars to
form.
Iron-carbon alloys, containing up to 2.06% of carbon, arc called Steels. Alloys, containing from 2.06 to
6.67% of carbon, experience eutectic transformation at (1147 C). The eutectic concentration of carbon
is 4.3% .
In practice only hypoeutectic alloys are used. These alloys (carbon content from 2.06% to 4.3%) are
called cast irons. When temperature of an alloy from this range reaches 2097 F (1147 C), it contains
primary austenite crystals and some amount of the liquid phase. The latter decomposes by eutectic
mechanism to a fine mixture of austenite and cementite, called ledeburite.
All iron-carbon alloys (steels and cast irons) experience eutectoid transformation at (723C), The
eutectoid concentration of carbon is 0.83%. When the temperature of an alloy reaches (723C),
austenite transforms to pearlite (fine ferrite-cementite structure, forming as a result of decomposition
of austenite at slow cooling conditions).

L- Liquid solution of carbon in iron


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-ferrite solid solution of carbon in iron. Maximum concentration of carbon in -ferrite is 0.09 % (14930C)
temperature of the peritectic transformation. The crystal structure of -ferrite is BCC.

Fig.: - iron (Ferrite) and its Microstructure


Austenite is an interstitial solid solution of carbon in -iron It has FCC (cubic face centered) crystal
structure, permitting high solubility of carbon up to 2.06% at (1147C). It does not exist below (723C)
and maximum carbon concentration at this temperature is 0.83 % .

Fig.: -iron (Austenite) and its Microstructure


ferrite is a solid solution of carbon in -iron. It has BCC crystal structure and low solubility of carbon
up to 0.25 % at (723C). It is exists at room temperature.
Cementite iron carbide, intermetallic compound, having fixed composition Fe3C. It is a hard and brittle
substance, influencing on the properties of steel and cast irons.

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Fig.: Allotropic forms of iron

Fig. Cooling curves for pure iron showing allotropic behavior of iron
Isomorphous systems contain metals which are completely soluble in each other and have a single type
of crystal structure. It is important to note that metals often show polymorphism: different structures
are more stable at different temperatures. For instance, -Fe, which is BCC, is stable up to 906C, -Fe,
which is FCC, is stable up to 1401C, and then -Fe is stable again up to the melting point at 1530C. A
third form of iron, -Fe, is HCP, and may be formed at high pressures.

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3.3 METALLIC MATERIALS AND THEIR HEAT TREATMENTS


The Nature of Metals
Characterized by:
1. Valence electrons of 1,2 or 3 see periodic table
2. Primary bonding between electrons called metallic bonding: Valence electrons not
bonded to particular atom but shared and free to drift through the entire metal

Fig.: Electron matrix of a metal atom and crystalline structures (i.e. metals) atoms are arranged in unit
cells 4 common cells shown above

3. Properties include: good conductors of electricity and heat, not transparent, quite
strong yet deformable
4. How do Metal Crystals Fail? Answer: Slip due to dislocations

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3.3.1 FERROUS METALS


Ferrous metals are those that contain iron as the base metal. The properties of ferrous metals may be
changed by adding various alloying elements. The chemical and mechanical properties need to be
combined to produce a metal to serve a specific purpose. The basic ferrous metal form is pig iron from
the blast furnace.

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Fig.: Iron Iron carbide phase equilibrium diagram illustrating ferrous metal carbon ranges
This figure strictly should be called the iron iron carbide diagram but conventionally it is called the
iron-carbon phase diagram. It seems to be the same as in the case of two components partially miscible
in solid state.
The difference is the structural changes resulting from iron being allotropic - that is, it can exist in more
than one form. These structural changes take place at 9100C and 14000C:
-

Below 9100C, the iron forms BCC crystals

From 9100C to 14000C, it forms FCC crystals

Above 14100C, it reverts to BCC crystals.

These lattice changes of structure are accompanied by change in volume as the atoms in crystal lattice
rearrange themselves.
When carbon content is less than 0.005% in Fe C alloys at room temperature, they are considered to
be pure iron (soft, ductile and weak) it is used only for magnetic devices.

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Steels have low carbon limits approximately 0.06 2%C. Fe C alloys with carbon content greater than
2% are Cast irons; above this carbon level casting is about the only way that a useful shape can be made
since the high carbon makes the iron alloy too brittle for rolling, forming, shearing or other fabrication
techniques.
Phase

Carbon
solubility

Name

Structure

Ferrite

Low,
up
to
0.0218 wt. %C %

-iron

BCC

Austenite

Up to 2.11 wt.
%C

-iron

FCC

Cementite

Fe:C = 3:1

Fe3C

Intermetallic
orthorhombic

Pearlite

Fixed C. content
(e.g.:0.76%)

Alternating
layers ,Fe3C

Temp

>727C

<727C

Strength

Ductility

Weak

Very ductile

Weak

Very ductile

Strong

Low
brittle

Btn
Fe3C

and

ductility,

Btn and Fe3C

Table: Allotropic forms of Iron


Terms: Eutectoid point - 3 phases (ferrite, austenite, and cementite) in equilibrium at one temperature.
All phases are solid; therefore this is a solid-solid transformation.
Eutectoid composition - 0.76% carbon (approximately a 1080 steel)
Eutectoid Structure - Pearlite
Proeutectoid - phase that forms at temps above the eutectoid temperature (727C). For hypoeutectoid
steels (steels with less than 0.76% C), ferrite is the proeutectoid phase. For hyper eutectoid steels
(steels with more than 0.76% C, cementite is the proeutectoid phase.
Hypoeutectoid is an iron carbon alloy
Ferrite ( phase): this is a week solution of carbon in BCC crystals of iron. There is a maximum of 0.03%C
in solid solution at 7230C, falling to 0.006%C in solid solution at room temperature (for all practical
purposes, it may be considered as pure iron). It is very soft, ductile and with relatively low strength.
Austenite ( phase): this is much more concentrated solid solution of carbon in iron than ferrite. It is
formed when carbon dissolves in FCC crystals of iron in the solid state. The maximum carbon which can
be held in solution with iron in solid state is 1.7% at 11470C. (For all practical purposes there is no
advantage in increasing the carbon content beyond about 1.2 1.4%)

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Cementite (Iron carbide phase): an excess of carbon combines with iron to form iron carbide (Fe3C).
This is true up to the limit of 1.7%C at room temperature, beyond which the excess carbon is
precipitated out as free or uncombined carbon flakes of graphite.
Thus, steels can be defined as those alloys of iron and carbon in which the entire carbon content is
combined with the iron in solid solution or as iron carbide (or both) and that no free carbon is present.
Since the maximum amount of carbon which can combine totally with iron is 1.7%; it follows that any
carbon in excess of this figure will precipitate out as graphite flake and the resulting material will not be
steel but cast iron.
The solid solution of austenite transforms to ferrite and Cementite at the eutectoid point of 723 0C when
0.83C is present. The crystals which are precipitated out have a lamellar structure consisting of alternate
layers of ferrite and Cementite. This lamellar structure is referred to as Pearlite and it is the toughest
structure which can exist in plain carbon steels. When the carbon content is 0.83%, the steel consists
entirely of Pearlite and it has maximum toughness. Steels with C</> 0.83 are Hypo/hyper-eutectoid
steels.

Fig.: Steel and cast iron ranges


1.1.1 FERROUS METALS
1.1.1.1 CAST IRON: Cast iron is a ferrous metal and is widely used. It is a hard, brittle metal that has
good wear resistance. Cast iron is the name given to those ferrous metals containing more than 1.7 %
carbon. It is similar in composition to crude pig iron (iron in rough form: a crude form of iron made in a
blast furnace and shaped into rough blocks for storage or transportation) as produced by the blast
furnace. Unlike steel, it is not subjected to an extensive refinement process. After the pig iron has been
remelted in a cupola furnace ready for casting, selected scrap iron and scrap steel are added to the melt
in order to attain targeted carbon concentration that eventually pertains to wanted compositional
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properties. Since pig iron and scrap are cheap and no expensive refinement process; cast iron is a useful
low cost material compared to steel. Hence, despite its relatively low strength and brittleness, they are
extensively used as engineering materials, following their cheapness, ease of melting and casting (high
fluidity makes it easy to cast into intricate shapes); very good machineability and a high damping
capacity when resistance to wear and compressive strength are required.
It will be noticed that a eutectic of austenite and cementite which contains 4.3% carbon is formed at
1131 C. (This eutectic point, like the eutectoid composition in the case of steel at 0.83% carbon, may be
moved farther to the left of the diagram by the elements present, so that a cast iron containing less than
4-3% carbon may be of eutectic composition)

Fig.: The phase equilibrium diagram of the iron.


It is widely used where castings of high rigidity, resistance to wear and compressive strength and of
complex shapes are required because of its ability to flow easily (high fluidity: its melting temperature is
between 1147 to 12500C which is substantially lower than that for mild steel)
Properties of cast Iron:

It can be casted to any shape

It is weak in tension but strong in compression and hence used in machine beds, which bears the
whole of structural weight of a machine without affecting the operators accuracy.

It has poor ductility and malleability

It offers good resistance to bending

It is brittle metal and should be carefully handled to avoid breakage


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It withstands high temperature

It easily rusts. It can be alloyed to be high resistant to corrosion.

Uses of cast iron:


Cast iron has high compression strength and due to its cheapness it is suitable for beds of machine tools
such as lathe, planning, shaping, milling, grinding, etc. it is also used in step-pulleys, piston rings, gear
boxes, body of electric motors, pumps, valves, hydraulic equipments, etc.
In production of cast iron and steel, the melt crosses a line of phases with different properties from
liquid to solid states: Austenite( phase solution):, cementite(Fe3C), ferrite( phase), pearlite. Four
involved intermediate phases are noteworthy to understand (that will be thoroughly detailed in
metallurgy):
Austenite ( phase solution): much more concentrated solid solution of carbon in FCC crystals of iron,
the maximum amount of Carbon which can be held in solid solution as austenite is only 1.7%C, i.e. the
maximum amount of carbon which can combine totally with iron is 1.7%.
Cementite (Fe3C): It is obvious the surplus carbon will combine with the iron to form iron carbide or it
can be precipitated out as flake graphite (graphite is an allotrope of carbon) due to the instability of
Cementite caused by some impurities as silicon. In the foundry, Cementite is referred to as combined
carbon and flake graphite is known as Free carbon or uncombined carbon flakes.
Ferrite ( phase) is a week solution of carbon in BCC crystals of iron. <0.02%C in solid solution at room
temperature for all practical purposes, it may be considered as pure iron. It is very soft, ductile and
with relatively low strength.
Pearlite: The solid solution of austenite, depending on subjected cooling procedure, may precipitate out
into a tough lamellar structure consisting of alternate layers of ferrite and Cementite.
Cast irons can be categorized into 4 types that can be expounded from the cooling phase diagram of the
blast furnace product.

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Fig.: CI section of the Iron-Carbon phase equilibrium diagram.


At the carbon concentration 4.3%C, the molten metal at 11470C austenite ( phase)+Cementite.
Unless, cooling is very rapid, Cementite graphite due to the Cementite instability caused by some
impurities such as silicon.
As cooling proceeds, austenite further graphite. At 7230C, providing cooling is slow enough the
remaining austenite into ferrite + large flake graphite together with fine flake of graphite from
Cementite decomposition after solidification. If at 7230C the cooling is sufficiently fast to prevent phase
equilibrium, the austenite ferrite and Pearlite as the Cementite essential for the formation of Pearlite
will be retained. With even faster cooling, the structure will consist of flake graphite in a matrix which is
entirely pearlitic called Grey cast irons.
1) Grey cast iron: Ferritic and pearlitic cast iron containing free graphite flakes are called Grey cast
irons because of the grey appearance of their surfaces when freshly fractured. Alloying addition of Si
(1-3wt.%) is responsible for decomposition of cementite, and also high fluidity. Thus castings of intricate
shapes can be easily made. Due to graphite flakes, gray cast irons are weak and brittle, relatively soft,
easily machined and welded. However they possess good damping properties, and thus typical
applications include: base structures, bed for heavy machines, engine cylinder blocks, pipe, and machine
tool structures etc. they also show high resistance to wear.
As in steel, increase of Pearlite enhances the toughness and hardness of Cast iron. With even faster
cooling (chilling) a different type of structure is likely to be formed. When the solidus temperature of
11470C is reached, the structure will consist entirely of austenite and Cementite. On further cooling the
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austenite changes into Pearlite, thus at room temperature the composition of the iron is Pearlite and
Cementite, White Cast Iron due to its white appearance when freshly fractured. The hardness of
Cementite makes it difficult to machine and its use is limited mainly where abrasion and wear resistance
is required. It has a high compressive strength, and when its annealed, it becomes malleable cast iron.
2) White irons: They are exceptional alloy hard, but brittle and not weldable. It is not often used,
except as the basis for the production of malleable irons by heat treatment, although portions of many
sand castings are made to solidify while, by the insertion of cells in the sand mould, in order to produce
hard and wear resistance surfaces in parts of the casting. Hence their use is limited to wear-resistant
applications such as rollers in rolling mills.
3) Malleable cast iron: As their name implies, malleable cast irons have increased malleability and
ductility, increased tensile strength, and toughness. Produced from white cast irons by a variety of heattreatment processes, namely black-heart, white heart and pearlitic processes; all these processes
consists in heating up to 800-9000C, then cooling white cast iron very slowly over a long period of time
depending upon the final composition and structure required. High temperature incubation causes
cementite to decompose and form ferrite and graphite. Thus these materials are stronger and tougher
than white cast iron with appreciable amount of ductility. It can be welded, machined, is ductile, and
offers good strength and shock resistance. Typical applications of malleable cast irons include: railroad,
connecting rods, marine and other heavy-duty services.
4) Nodular cast iron (duty iron/ductile or Spheroidal graphite iron): Alloying additions are of prime
importance in producing this materials. Small additions of Mg or Ce (cerium from Lanthanide series) to
the gray cast iron melt before casting can result in graphite to form nodules or sphere-like particles. The
graphite flakes become redistributed throughout the mass of the metal as fine spheroids of graphite. It
gets this name because its carbon is in the shape of small spheres, not flakes. This makes it both ductile
than gray cast irons and malleable. Its also stronger and weldable. Matrix surrounding these particles
can be either ferrite or pearlite depending on the heat treatment. Typical applications include: pump
bodies, crank shafts, automotive components, etc.
5. Chilled cast iron: In some castings, in order to have a hard durable surface, the casting is chilled. Such
castings are produced by burying iron plates in the mould; as a result, the metal coming in contact with
these plates will be cooled rapidly and will be harder than the rest of the casting. Chilled castings are
used to some extent as wheel of rail road cars.
INFLUENCE OF ALLOYING ELEMENTS ON THE PROPERTIES OF CAST IRON
Carbon: in the cast iron the carbon may be present in two forms: as free carbon/graphite, and as a
combined carbon/iron carbide. Cast iron in which entire carbon is in free State is called grey cast iron. It
is soft and easily machinable. When the carbon is in the combined state in the form of iron carbide, we
get white cast iron. It is hard, brittle and un-machinable.
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To heighten their adaptability, they are not solely alloys of iron and carbon but complex alloys in which:
- Earth-extracted impurities such as sulphur (maintained below 0.1% for the most foundry purposes as
too much sulfur trigger unsound casting. It makes the cast iron hard and brittle) and phosphorus (rarely
allowed to surpass 1%. It contributes fusibility and fluidity but induces brittleness)
- Alloy elements with a significant influence on the properties of the casting such as Silicon: up to 3%
concentration. It provides the formation of free graphite soft black form of carbon; i.e. a soft dark
carbon that conducts electricity, occurs naturally as a mineral and also produced industrially. Use:
batteries, lubricants, polishes, electric motors, nuclear reactors, carbon fibers, pencil lead which makes
the iron soft and ease machinable. It also produces sound castings free from blow holes, because of its
high affinity for oxygen. It can also be alloyed with Manganese: often kept below of 0.75%, it makes the
cast iron white and hard.
Alloying elements
Silicon
Sulphur
Manganese

Phosphorus
Nickel

Chromium
Molybdenum

Characteristics resulting from the alloying elements added


Machineability, Softener: promotes flake graphite at expense of cementite
Hardens: stabilizes cementite and prevents the formation of flake graphite,
embrittlement due to FeS
Strengthens by grain refinement, Desulphuriser (MnS is insoluble in molten iron
then floats to join slag), it hardens when it is in excess, promotes fluidity then
sound casting
High intricate ornamental casting by its fluidity, makes iron spongy and porous,
embrittlement like S
Increases density and strength and improves wearing qualities and raises the
machineability, promotes the formation of free graphite, thus it toughens the
casting
corrosion resistance at high temperatures, hardness and wear resistance by
stabilizing the combined carbon (cementite)
Stiffness and tensile strength, hardness by doubling carbides if it is added at larger
amounts, prevents decay at high temperature in castings of Ni and chromium.

Vanadium

Strength and hardness, stabilizes the carbides and reduces their tendency to
decompose at high temperature so used in heat resisting castings

Copper

Reduces the effects of atmospheric corrosion even if it is insoluble in iron


(sparingly used because it is only slightly soluble in iron)

Martensite cast iron (46%Ni, 1%Cr)

Reduces the possibility of cracking and distortion bse it is not quench hardened
so used in abrasion resisting components. Machined by grinding

Austenite Cast iron (1120%Ni and up to 5%Cr)

Corrosion and heat resistance, non magnetic.

Table 3: Summarized alloying elements in cast iron and their effects


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1.1.1.2 STEELS
Steel is made by oxidizing away the impurities that are present in the iron produced in the blast furnace.

Fig.: Iron carbon phase equilibrium diagram (steel section)


Eutectoid Microstructures: Just like the eutectic systems there are a number of different morphologies
for the two phases in a binary eutectic alloy. The most common morphology for eutectoid areas in the
Fe-Fe3C system is lamellar. (This is because most steel is relatively slowly cooled through the eutectoid
phase transformation.)

Fig.: Eutectoid Microstructures

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Fig: Development of hypo and hypereutectoid steel

Fig.: Slow Cooling of Plain-Carbon Steels: Transformation of a 1.2% C hypereutectoid and 0.4% C
hypoeutectoid with slow cooling.
Problems
(1) A 0.45%C hypoeutectoid plain-carbon steel is slowly cooled from 950 C to a temperature just
slightly above 723 C. Calculate the weight percent austenite and weight percent proeutectoid ferrite
in this steel.

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Figures for problem 1, 2 and 3


Problem 2 : A 0.45%C hypoeutectoid plain-carbon steel is slowly cooled from 950 C to a temperature
just slightly below 723 C. (a)Calculate the weight percent proeutectoid ferrite in this steel; (b) Calculate
the weight percent eutectoid ferrite and the weight percent eutectoid cementite in this steel.
Soln.: Proeutectoid Ferrite =(0.80-0.45)/(0.8-0.02) = 44.9%
Cementite = (0 45-0 02)/(6 67-0 02) 6 5%
Total ferrite = (6.67-0.45)/(6.67-0.02) = 93.5%
Eutectoid ferrite = total ferrite proeutectoid ferrite = 93.5 44.9 = 48.6%
Problem 2: Hypoeutectoid steel contains 22.5% eutectoid ferrite. What is the average carbon content?
Soln.: Total ferrite= proeutectoid ferrite + eutectoid ferrite (6.67-x)/(6.67-0.02) = (0.80 x)/(0.8-0.02) +
0.225X =0.2

Steel is an alloy of iron and carbon containing up to 1.7 % of carbon. When the alloying element is only
carbon, the steel is referred to as plain carbon steel and it is classified following the percentage of
carbon it contains:

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Low or soft Carbon Steel or mild steel (Carbon content up to 0.35 % C):
This steel is the softest and most ductile metal and can be rolled, punched,
sheared, and worked when either hot or cold. It is easily machined and can be
readily welded by all methods. It is used for rivets and solid drawn steel tubes
bolts, nuts, screws, shafts, couplings, water pipes, piston rods, lead screw of
lathe etc. It does not harden to any great amount; however, it can be easily
case- or surface-hardened
Properties of mild steel: i) It is strong in tension and compression, in shear and
hence used in rivets for light and heavy work. It processes high ductility,
malleability and toughness. (ii) It can be easily welded and forged and can be
produced in bar of any type. (iii) It can be easily machined.
Medium Carbon Steel (Carbon content from 0.35 to 0.65%C).
This steel may be heat-treated after fabrication. It is used for general machining
and forging of parts that require surface hardness and strength (with increasing
carbon content the strength and hardness increase but ductility decreases and
the welding properties and machineability become poorer).

It is made in bar form in the cold-rolled or the normalized and annealed condition. During welding, the
weld zone will become hardened if cooled rapidly and must be stress-relieved after welding.
High Carbon Steel (Carbon content from 0.65 to 1.7%)
This steel is harder and less tough. It used in the manufacture of drills, taps, dies, springs, and other
machine tools and hand tools that are heat-treated after fabrication to develop the hard structure
necessary to withstand high shear stress and wear. It is manufactured in bar, sheet, and wire forms, and
in the annealed or normalized condition in order to be suitable for machining before heat treatment.
This steel is difficult to weld because of the hardening effect of heat at the welding joint, except
grinding can be done only the annealed state.
Tool Steel (carbon content from 0.90 to 1.70 percent)
This steel is used in the manufacture of chisels, shear blades, cutters, large taps, woodturning tools,
blacksmiths tools, razors, and other similar parts where high hardness is required to maintain a sharp
cutting edge. It is difficult to weld due to the high carbon content. Tool steels are of two varieties: Plain
carbon tool steel, high speed steel
- Plain carbon steel (0.9 to 1.3% of carbon), it was at one time the only tool steel available, but its
use is newly restricted. These steels are cheap and harden at low temperature. They are used
for press tools and applications where the conditions are not severe.

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The cutting tool steels mostly used nowadays are high-speed steels. High-speed steel is a selfhardening steel alloy (18% tungsten, 4% chromium, 1% vanadium and about 1% carbon, and rest
iron) that can withstand high temperatures without becoming soft. High-speed steel is ideal for
cutting tools because of its ability to take deeper cuts at higher speeds than tools made from
carbon steel. High-speed steels are not exceptionally hard; in fact, plain carbon steel can easily
be made to give a greater hardness, but whereas the hardness of plain carbon steel will fall off
at temperature greater than about 2500C to 3000C, the high speed steels retain their hardness
up to about 6000C. They are used for tools for lathe, milling machine cutters, twist drills, files,
etc.

Wrought iron: Wrought iron is pig iron from which most of the carbon has been removed. It contains
only about 0.04% carbon. It is tough; however, it can be bent or twisted very easily. It is also corrosion
resistant. It was used mostly in ornamental ironwork, such as fences and handrails, because it is welded
or painted easily and it rusts very slowly; horses shoes, nails, chain and crane hooks, and door hardware
it has been largely replaced with the use of hot-rolled low-carbon steel.

Alloy Steels
Steel is manufactured to meet a wide variety of specifications for hardness, toughness, machineability,
resistance to corrosion, tensile strength, and so forth. Manufacturers use various alloying elements to
obtain these characteristics. Thus , Beside the carbon with its specific amount for each carbon steel
classification, other elements can be chiefly added to the iron so as to provide excellent mechanical
properties for structural materials alloys steels.
Alloys steels are classified into two major types depending on the structural classification:
Low alloy steels
Low alloy steels contain a few percent (typically between 1 and 7%) of elements such as Cr, Ni, Mo and V.
This category includes chromium steels (containing up to 5% Cr and 1% Mo) and nickel steels (containing
up to 5% Ni).
Low alloy steels are generally weldable by most processes, as long as adequate precautions (important
to know the composition of the material) are taken to avoid defects, but it is important to know the
service, joint configuration and the subgroup of the material type.
High alloy steels
(i) High-speed tool steels
Tungsten and chromium form very hard and stable carbides. Both elements also raise the critical
temperatures and, also, cause an increase in softening temperatures. High carbon steels rich in
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these elements provide hard wearing metal-cutting tools, which retain their high hardness at
temperature up to 600C. A widely used high-speed tool steel composition is containing 18% of
tungsten, 4% of chromium, 1% of vanadium and 0.8% of carbon .
It is a subset of tool steels, commonly used in tool bits and cutting tools. It is often used in power saw
blades and drill bits. It is superior to the older high carbon steel tools used extensively through the
1940s in that it can withstand higher temperatures without losing its temper (hardness). This property
allows HSS to cut faster than high carbon steel, hence the name high speed steel. At room temperature,
in their generally recommended heat treatment, HSS grades generally display high hardness (above
HRC60) and abrasion resistance (the process of wearing away by friction).
generally linked to tungsten and vanadium content often used in HSS) compared to common carbon and
tool steels.)
Tungsten Carbide
Tungsten carbide is the hardest man-made metal. It is almost as hard as a diamond. The metal is molded
from tungsten and carbon powders under heat and pressure. Tools made from this metal can cut other
metals many times faster than high-speed steel tools.
(ii) Stainless steels
When chromium is present in amounts in excess of 12% , the steel becomes remarkably anticorrosive,
owing to protective film of chromium oxide that forms on the metal surface. There are several types of
stainless steels, and these are summarized below:
a) Ferritic stainless steels contain between 12- 25% of chromium and less than 0.1% of carbon.
b) Martensitic stainless steels contain between 12-18 % of chromium, together with carbon contents
ranging from 0.1 to 1.5 %
c) Austenitic steels contain both chromium and nickel. When nickel is present, the tendency of nickel to
lower the critical temperatures over- rides the opposite effect of chromium, and the structure may
become wholly austenitic.
(iii) Merging steels
These are very high-strength materials that can be hardened to give tensile strengths up to
1900MPa .They contain 18% of nickel, 7% of cobalt and small amounts of other elements such as
titanium, and the carbon content is low, generally less than 0.05% . A major advantage of merging
steels is that after the solution treatment they are soft enough to be worked and machined with
comparative ease.

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ALLOYING ELEMENTS IN CARBON STEEL


Mostly used elements with the alloy steel are: 2 % Manganese(Mn); 0.5 % Chromium(Cr) or Nickel(Ni);
0.3 % Tungsten(W) or Cobalt; 0.1 % Molybdenum(Mo) or Vanadium; Different amount of Aluminum(Al),
Copper(Cu) and Silicon(Si).
The alloying elements in cast irons are similar to those in alloy steels, which are as follows:

Nickel: This is used for grain refinement (In polycrystalline materials, each separate crystal is called
a grain and the areas of mismatch between adjacent crystals are called grain boundaries), to add
strength, and to promote the formation of free graphite. Thus it toughens the casting.

Chromium: This stabilizes the combined carbon (cementite) present and thus increases the
hardness and wear resistance of the casting. It also improves the corrosion resistance of the
casting, particularly at elevated temperatures. As in alloy steels, nickel and chromium tend to
be used together because they have certain disadvantages when used separately which tend
to offset their advantages. However, when used together the disadvantages are overcome, whilst
the advantages are retained.

Copper: This is used very sparingly as it is only slightly soluble in iron; however, it is useful in
reducing the effects of atmospheric corrosion.

Vanadium: This is used in heat-resisting castings as it stabilizes the carbides and reduces their
tendency to decompose at high temperatures.

Molybdenum: it dissolves in the ferrite and, when used in small amounts (0.5 %), it improves the
impact strength of the casting. It also prevents decay at high temperatures in castings containing
nickel and chromium. When molybdenum is added in larger amounts it forms double carbides,
increases the hardness of castings with thick sections, and also promotes uniformity of the
microstructure.

Types of steel

Characteristics resulting from the Applications


added alloying elements
Carbon steels
Surface hardness and strength
Nickel steels
Toughness, prevent rusting but
reduces the coefficient of
expansion
strength
without
lowering ductility
Invar (0.3 to 0.5% C, 0.5%Si,
Idem
Precision work: measuring
0.3% Mg, S and P traces, 28 to
tapes, chains, wires and time
32%Ni)
measuring instruments.
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Chrome-Nickel steels
Molybdenum steels

Toughness and depth hardness


Eliminate
brittleness
and
increases Depth hardness
Chrome-Molybdenum steels
High strength and toughness
Chromium steels
Corrosion and wear resistance
and hardness and tensile strength
Vanadium steel
Tensile strength, resistance to
chock and abrasion
ChromeVanadium (0.5 to 1.5% Depth hardness and toughness at
chromium, 0.05 to 0.35%V and sub-zero temperature, good
0.13 to 1.5%C
tensile
strength,
ductility,
elasticity and endurance
Stainless steel (4 to 22% of Excellent corrosion, high polish.
chromium and 0 to 26% nickel). N.B: If the maximum ductility is
required, the carbon content
must be kept low. heat
resistance by addition of about
3% of silicon

Gears and axles

Tungsten steels

Permanent magnets (4 to 5%
tungsten and 0.5 to 0.7%
carbon)
General purpose steel

Chrome-Nickel-Molybdenum
steels
Manganese steel (>1%Mg))

Hardness at high temperature,


fine
dense
structure
and
toughness
Toughness and strength

Piston rods, crank ins, axles,


springs.
gears and automobile parts

Chemicals dyeing and food


handling plants and for surgical
instruments. For cutlery and
engineering purposes no nickel
but chromium content is 12
14% and the carbon 0.3
0.55%.

Toughness,
abrasion.
desulphuriser

resistance
to Machinery parts subjected to
Deoxidizer, severe wear, as crushing and
grinding machinery and in
railways crossings.
Silicon-Manganese steels (1.25 Depth hardness and toughness Springs
to 2.5% Si, 0.5 to 0.65%C, 0.6 to under impact and fatigue
0.9% Mg)
resistance
Table: general characteristics of common alloys
Glossary about effects of alloying elements in steel
In general, alloying elements are added to steels in order to accomplish the following purposes:
-

To improve the mechanical properties of the steel by improving its micro-structure.


To improve the resistance of steel to corrosion and oxidation.

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To develop special properties such as: magnetic and electrical characteristics; high strength at
high temperature; steels that are austenite at room temperature
To stabilize the iron-carbide in steel by adding chromium, vanadium, titanium, manganese,
tungsten, or molybdenum in varying amounts, depending on the end use of the product.
To promote graphitization by the addition of silicon, aluminium or copper.

Effect of alloying elements in low-alloy steels


The two phases that commonly present in low-alloy steels are ferrite and carbide.
a) In the ferrite phases; silicon, aluminum, copper nickel, cobalt, zirconium and phosphorus.
b) In the carbide phases; manganese, chromium , molybdenum, tantalum, vanadium, columbium
and titanium
These alloying elements have the following effects on the steel.
-

Nickel: In amount of from 30 t0 50 per cent reduces the thermo expansion and magnetic
permeability of alloys, while from 1 to 5 per cent it increases the hardenability. It has also the
characteristics of graphitizing and producing a corrosion resistant, tough steel alloy. In addition,
it slows down the austenite to pearlite transformation.
Cobalt: It improves high temperature properties of steel. It also added to high speed, heat
resistant steel, tending to decrease hardenability in steel.
Chromium: Provides effective corrosion and oxidation resistance. In addition it improves the
wear resistance of steels and increases its hardenability.
Aluminum: Is usually added to produce the completely deoxidized, killed steel. It also increases
steels resistance to oxidation.
Manganese: In amount of 0.30 to 1.50 per cent is a good deoxidizer, while in high amounts it
increases the hardenability of steel.
Molybdenum (also titanium, niobium, and vanadium): Increases the wear resistance and
strength of the steel at high temperature. It also increases hardenability.
Copper: Is used mainly to improve corrosion resistance, for it dissolves only in the ferrite and
does not form carbides. It improves also machinability of steel.
Lead: In a small amounts however like copper, it improves the machinability of steel.
Sulfur: Improves the machinability of steel in amounts of from 0.10 to 0.30 per cent, together
with 0.60 to 1.50 per cent of manganese, by means of deformation of manganese sulfide.
Phosphorus: Is used to increase corrosion resistance of steel in some structural grades, when in
a present of small amount of copper.
Silicon: Dissolve mainly in the ferrite and it has a substantial strengthening effect

HOW MATERIALS ARE STRENGTHENED?


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1. Work hardening: (a) Cold working result in creation of more dislocations which strengthen the
material
2. Solid solution strengthening: Substitutional or interstitial atoms cause lattice distortion, hindering
movement of dislocation.
3. Grain size refinement: the finer the grain size the higher the strength (Hall-Petch equation)
4. Transformation hardening
5. Irradiation hardening and 6. Dispersion (Age or precipitation) hardening: Formation of a secondary
phase that distorts lattice and blocks dislocation movement. Precipitation hardening is also called age hardening
because it involves the hardening of the material over a prolonged time. The precipitates form when the solubility limit is exceeded.
Small inclusions of secondary phases strengthen material. Lattice distortions around these secondary phases impede dislocation motion

Fig.5.9: Precipitation hardening


Solution heat treatment: at To, all the solute atoms A are dissolved to form a single-phase () solution.
Rapid cooling: across the solvus line to exceed the solubility limit. This leads to a metastable
supersaturated solid solution at T1. Equilibrium structure is +, but limited diffusion does not allow
to form.
Precipitation heat treatment: the supersaturated solution is heated to T2 where diffusion is appreciable
phase starts to form as finely dispersed particles: ageing
Dispersion and Precipitate Strengthening (aka Heat Treat):
Left figure is dispersion and precipitate strengthening and right is solution hardening (alloying)

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Fig.: Heat Treatment for Precipitation Hardening

Fig.: Interstitial and substitutional solid solution

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Fig.: How to strengthen metals

HEAT TREATMENT OF METALS


Heat treatment is any one of a number of controlled heating and cooling for the primary purpose of
altering physical properties to the desired ones or combination of properties suitable for the particular
application of a metal. I.e. Its purpose is to improve the structural and physical properties for some
particular use or for future work of the metal. Heat treatment is sometimes done inadvertently due to
manufacturing processes that either heat or cool the metal such as welding or forming.
Purposes of heat treatment
a) To relieve the stress set up in the material after hot or cold working in order to improve
machinability.
b) To improve mechanical properties like tensile strength, hardness, ductility, shock resistance etc.
c) To modify the structure of the material to improve its electrical and magnetic properties.
d) To increase the qualities of a metal to provide better resistance to heat, corrosion and wear.
e) To change grain size.
f) To eliminate the effects of cold working and give a more uniform grain size.
g) To soften them for easy machining or cutting operation.
There are five basic heat treating processes: hardening, case hardening, annealing, normalizing, and
tempering. Although each of these processes bring about different results in metal, all of them involve
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three basic steps: heating, soaking, and cooling


Heating
Heating is the first step in a heat-treating process. Many alloys change structure when they are heated
to specific temperatures. The structure of an alloy at room temperature can be a mechanical mixture, a
solid solution, or a combination solid solution and mechanical mixture.
A mechanical mixture can be compared to concrete. Just as the sand and gravel are visible and held in
place by the cement. The elements and compounds in a mechanical mixture are clearly visible and are
held together by a matrix of base metal. A solid solution is when two or more metals are absorbed, one
into the other, and form a solution. When an alloy is in the form of a solid solution, the elements and
compounds forming the metal are absorbed into each other in much the same way that salt is dissolved
in a glass of water. The separate elements forming the metal cannot be identified even under a
microscope. A metal in the form of a mechanical mixture at room temperature often goes into a solid
solution or a partial solution when it is heated. Changing the chemical composition in this way brings
about certain predictable changes in grain size and structure. This leads to the second step in the heat
treating process: soaking.
Soaking
Once a metal part has been heated to
the temperature at which desired
changes in its structure will take place, it
must remain at that temperature until
the entire part has been evenly heated
throughout. This is known as soaking.
The more mass the part has, the longer it
must
be
soaked.
The
critical
temperatures of soaking are determined
according to the following critical
temperatures.
Fig.: Soaking temperatures used in heat treatments
Lower critical temperature: A1 below which austenite does not exist
Upper critical temperature: lines, A3 and Acm above which all material is austenite
Cooling
After the part has been properly soaked, the third step is to cool it. Here again, the structure may
change from one chemical composition to another, it may stay the same, or it may revert to its original
form. For example, a metal that is a solid solution after heating may stay the same during cooling,
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change to a mechanical mixture, or change to a combination of the two, depending on the type of metal
and the rate of cooling. All of these changes are predictable. For that reason, many metals can be made
to conform to specific structures in order to increase their hardness, toughness, ductility, tensile
strength, and so forth.
Heat treatment processes
1. Annealing
2. Spheroidizing
3. Normalizing
4. Hardening
5. Tempering
6. Case hardening or surface hardening
a. Carburizing
d. Induction hardening
b. Carbonitriding
e. Flame hardening
C. Nitriding
f. laser hardening
1. ANNEALING: It is the process of softening of hard metal by heating to a high temperature followed by
slow cooling.
Purposes of annealing:
a) To soften a steel or metal piece so that it may be more easily machined or cold worked, make
them more ductile and tough.
b) To relieve internal stresses caused by cold working of metal, hence restore ductility of cold
worked steels
c) To refine the grain size and structure to improve mechanical properties.
d) To homogenize the structure and prepare for subsequent other heat treatments (Machining
finish taken by annealing surface is not as good as of normalized steel surface)
e) To remove gases trapped in the metal during initial casting
Processes involved in annealing:
(a) Heating the steel to a prescribed temperature 300C to 500C above the upper critical temperature
for hypo-eutectoid steel and by the same temperature above lower critical temperature for
hyper-eutectoid steels. Heating produces austenite or austenite along with cementite and very
slow cooling produces soft pearlite mixed with ferrite or cementite depending upon carbon
percentage of steel
(b) Holding it for some for the required period of time at the temperature so that internal changes
may take place. The time allowed is 1 to 2 minutes for each mm of section of the piece being
annealed.
(c) Allow it to cool down slowly back to room temperature. Steel must be cooled very slowly to
produce maximum softness. This can be done by burying/dipping the hot part in sand, ashes, or
some other substance that does not conduct heat readily (packing), or by shutting off the
furnace and allowing the furnace and part to cool together (furnace cooling).
Medium
Severity of quenching
hardness
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Air

Small

Small

Oil

Moderate

Moderate

Water

Large

Large

Table: Effect of Quenching Medium


Types of annealing heat treatments:
a) Full annealing: austenizing and slow cooling (several hours). Produces coarse pearlite (and possible
proeutectoid phase), that is relatively soft and ductile. Is used to soften pieces which have been
hardened by plastic deformation, and which need to undergo subsequent machining/forming.
b) Process annealing
c) Spheroidize annealing (to improve machinability, pearlite structure changes from lamellar to global). A
prolonged heating just below the eutectoid temperature results in the soft spheroidite structure. This
achieves maximum softness needed in subsequent forming operations.
d) Isothermal annealing
e) Homogenizing
Normalize: fine pearlite, full anneal: coarse pearlite

Fig.: Cooling Curves: Fe-C System

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(a)

(b)

Soaking

A3

1
Slow cooling to Room
500-7000C Heating
temperature c<0.8%

A1

Soak

Cool slowly

Hypereutectoid
steels c>0.8%
Time

1100-12000C

(c)

A3

A1

A1

(d)
6-8 hours
Air Cooling

600 C

A3

Soak 1

Dissolution into

A1
Soak 2

(e)

Complete to P
Quenching
transformation

Fig.: Annealing processes


2. SPHEROIDIZING: It is the process of producing globular form of cementite in the structure of high
carbon steel in order to improve its machinability. After it has been full annealed or hardened, it is
heated slowly to a temperature below the lower critical (650-700) temperature and held there for a long
time, the spheroidal type of structure will be obtained.
3. NORMALIZING: Ferrous metals are normalized to relieve the internal stresses produced by machining,
forging, or welding and to improve machinability. Normalizing is used to refine the structure of the steel
to improve machinability, tensile strength, structure of weld and remove strains caused by cold working
processes. It removes the dislocation caused in the internal structure of the steel due to hot working.
Normalized steels are harder and stronger than annealed steels. Steel is much tougher in the normalized
condition than in any other condition. Parts that will be subjected to impact and parts that require
maximum toughness and resistance to external stresses are usually normalized. Normalizing prior to
hardening is beneficial in obtaining the desired hardness, provided the hardening operation is
performed correctly. Low carbon steels do not usually require normalizing, but no harmful effects result
if these steels are normalized.
Processes involved in normalizing:
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Heating a metal piece to a temperature just above (300C to 500C, that temp. is higher than either
the hardening or annealing temperatures) the upper critical temperature to reduce grain sizes
(of pearlite and proeutectoid phase) and make more uniform size distributions.
- It is kept at that temperature for about 15minutes and then allowed to cool down in air. This
process provides a homogeneous structure in low and medium carbon steels. The homogeneous
structure provides a high yield point, ultimate tensile strength and impact strength with lower
ductility to steels. Heating produces austenite and cooling produces finer pearlitic structure as
compared to annealing along with ferrite or cementite depending upon the carbon percentage
of steel.
Machining finish taken by the surface of normalized steels is generally better.
-

4. HARDENING: A ferrous metal is normally hardened by heating the metal to the required temperature
(300C to 500C above the upper critical temperature) for both hypo and hyper-eutectoid steel. Depending
upon its thickness, it is held at this temperature for a time and then rapidly cooled by plunging the hot
metal into a suitable cooling medium like water, oil, brine, or a current of air from blower or compressor.
To harden low and medium carbon steel, a very rapid quenching rate is necessary like quenching, in
water baths. But oil is generally used as the quenching medium for high carbon and many alloy steels.
The rapid cooling, convert most of the austenite into martensite which is hard and more stable than
austenite at ordinary temperatures.
The hardening process increases the hardness (wear resistance) and strength of metal, but also
increases its brittleness.
5. TEMPERING
Steel is usually harder than necessary and too brittle for practical use after being hardened. Severe
internal stresses are set up during the rapid cooling of the metal. Steel is tempered after being hardened
to relieve the internal stresses and reduce its brittleness.
Tempering is the process used to impart toughness to steel while retains most of hardness to increase
its usefulness by improving its shock resistance. Tempering requires the reheating of steel after being
hardened to temperature below its lower critical temperature followed by a fair rapid cooling in water
or oil.
Tempering consists of heating the metal to a specified temperature and then permitting the metal to
cool. The rate of cooling usually has no effect on the metal structure during tempering. Therefore, the
metal is usually permitted to cool in still air. Temperatures used for tempering are normally much lower
than the hardening temperatures. The higher the tempering temperature used, the softer the metal
becomes. High-speed steel is one of the few metals that become harder instead of softer after it is
tempered.
- Low tempering: only for stress relief, obligatory for hardened metals
- Medium temperature tempering: Reduces hardness by transforming martensite to Bainite.
Toughness and ductility are increased.
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High tempering temperature: almost all martensite is transformed to Bainite and fine pearlite.
Material is very ductile and tough, with improved fatigue properties.
Soaking

Soaking

A3
A1

Air cooling
Heating

A3
A1

c>0.8%

Hyper (c>0.8%) Quench in water


or oil

NORMALIZING
DIRECT HARDENING
- Stable

A3

650
500
450
0
350

A1

-P

Pearlite

-B

Bainite

High temp.
Medium temp.

250
150

Low temp.

Ms Unstable()
Mf

Martensitic
Water quench Oil quench Air cool

Furnace cool

TEMPERING

A3
A1

Pearlite
-B

Bainite

Ms
Mf
MARTEMPERING (martensite) AUSTEMPERING (Bainite)

Fig.: Normalizing, direct hardening, tempering, martempering and austempering


6. CASE HARDENING OR SURFACE HARDENING
Case hardening is an ideal heat treatment to produce a hard surface on ductile Steel for parts which
require a wear-resistant surface and a tough core, such as gears, cams, cylinder sleeves, and so forth.
During the case-hardening process, low-carbon steel (either straight carbon steel or low-carbon alloy
steel) is heated to a specific temperature in the presence of a material (solid, liquid, or gas) which
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decomposes and deposits hardener element into the surface of a steel. Then, when the part is cooled
rapidly, the outer surface layers or case becomes hard, leaving the, inside of the piece (inner cores) soft
but very tough.
6.1 CARBURIZING OF STEELS
It involves the introduction of additional carbon into the surface of mild steel, effectively producing a
composite material consisting of low carbon steel with a thin case, about 0.5 0.7 mm in thickness, of
high carbon steel, this was the principle of case-hardening that have been used for centuries in the
conversion of mild or wrought iron to steel by the cementation process.
In the carburization process for steel, carbon is introduced into the surface of low-carbon steel, typically
containing 0.1 to 0.2 % carbon. The carbon content of the carburized surface layer or case normally is
increased to about 0.8 to 1.0 % C. The carbon is introduced into the steel at temperatures above the
upper transformation temperature where the steel is FCC-austenitic.
The steel must be in the austenitic condition where there is appreciable interstitial solid solubility of
carbon in austenite. The solubility of carbon in iron varies with temperature, and in Fe-C alloys ranges
from about 0.8% at 723C to about 2.0% at 1148C. Alloying elements can affect the solubility of carbon
in iron. Below 723C, carbon has a very low solubility in BCC ferrite (about 0.02% maximum), and thus
carburizing is not possible. Carburizing is usually done in the 850 to 950C range, although temperatures
as low as 790C and as high as 1095C can be used.
Surface- hardening techniques for steels: gas carburizing, carbonitriding, nitriding, and induction surface
heating. Then localized surface-hardening techniques such as flame and laser hardening will be treated.
After carburizing, the workpiece is usually quenched to produce a martensitic structure in the case. Thus,
the carburizing treatment can produce steel with a hardened surface (case) and a core with low strength,
high ductility, and toughness typical of low-carbon steel.
The case-hardening consists in surrounding the component with suitable carbon material and heating it
to above its upper critical temperature for long enough to produce a carbon enriched layer of sufficient
depth.
The case-hardening process has
two distinct steps, as shown:
- Carburising ( the additional of
carbon)
- Heat treatment (hardening and
core refinement)

Fig:. Case hardening : (a) carburizing, (b) after carburizing, (c) after quenching component.
Solid, liquid and gaseous carburizing media are used. The nature and scope of the work involved will
govern which media is best to employ.
Applications:
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Carburizing is widely used in industry for machine components such as gears, bearings, and shafts where
surface resistance to wear and contact and bending fatigue is required. Carburizing is also used for
heavy-duty gears where good fracture toughness is needed in addition to wear and fatigue resistance.
The selection of steels for carburizing depends on many variables such as carbon and alloy content,
grain growth characteristics, machinability, and cost. Both plain-carbon and low-alloy steels containing
about 0.20% carbon are the most common carburizing steels. Plain-carbon steels are satisfactory for
many applications where distortion of the workpiece is not critical and where high-strength core
properties are not required. The most common alloying elements for carburizing steels are nickel (0.53.5%), chromium (0.4-1.4%), and molybdenum (0.1-0.3%). Steels containing (0.1-0.3%) sulfur are often
used for improved machinability.
Carburizing in solid media "Pack-carburizing"
As it is usually called, involves packing the components into cast-iron or steel boxes along with the
carburizing material so that a space of approximately 50 mm exists between the components. The lids
are then luted on to the boxes, which are slowly heated to the carburizing temperature for between 900
and 950 C. they are maintained at this temperature for up to five hours, according to depth of case
required.
Carburizing media vary in composition, but consist essentially of some carbonaceous material, such as
wood or bone charcoal or charred leathers together with an energizer which may account for up to 40%
of the total composition. This energizer is usually a mixture of sodium carbonate ("soda ash") and
barium carbonate, and its purpose is to accelerate the solution of carbon by the surface layer of the
steel. It is thought that carburization proceeds by dissociation of carbon monoxide which will be present
in the hot box. When the gas comes into contact with the hot steel it dissociates thus:
The atomic carbon deposited at the surface of the steel dissolves easily in the metal. In this method of
carburizing the thickness of the surface is between 0.05 1.55 mm. If it is necessary to prevent any
areas of the component from being carburized, this can be achieved by electro-plating these areas with
copper to a thickness of 0-075-0-10 mm; carbon being insoluble in solid copper at the carburizing
temperature.
When carburizing is complete the components are quenched or cooled slowly in the box, according to
the nature of the subsequent heat-treatment to be applied.
Carburizing in a liquid bath (Cyaniding)
Liquid-carburizing is carried out in baths containing from 20 to 50% sodium cyanide, together with up to
40% sodium carbonate and varying amounts of sodium chloride i.e. low carbon steel is immersed in a
molten salt bath consisting of Nacl, Na2C03 and Na CN. This cyanide-rich mixture is heated in pots to a
temperature of 870-950 C, and the work, which is contained in wire baskets, is immersed for periods
varying from about five minutes up to one hour, depending upon the depth of case required. The carbon
and especially the nitrogen diffuse into the surface of steel. Nitrides on the surface of steel make it
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compact and hard. There is no need of quench hardening.


The process is particularly useful in obtaining shallow cases of 0.1 0.25 mm. Dissociation of the carbon
monoxide at the steel surface then takes place with the same result as in pack-carburising. The nitrogen,
in atomic form, also dissolves in the surface and produces an increase in hardness by the formation of
nitrides as it does in the nitriding process.
Cyanides are, of course, extremely poisonous, and every precaution should be taken to avoid inhaling
the fumes from a pot. Every pot should be fitted with an efficient fume-extracting hood. Likewise the
salts s ho u ld in no circumstances be allowed to come into contact with an open wound. Needless to say,
the consumption of food by operators whilst working in the shop containing the cyanide pots should be
Absolutely forbidden.
This process has the following advantages over pack carburization: Bright finish work, avoid risk of
distortion and cracking, reduced surface oxidation One of the main advantages of cyanide-hardening is
that pyrometric control is so much more satisfactory with a liquid bath. Moreover, after treatment the
basket of work can be quenched. This not only produces the necessary hardness but also gives a clean
surface to the components.
Carburizing by gaseous media
Gas-carburizing is carried out in both batch-type and continuous furnaces. The components are heated
at about 900 C for three or four hours in an atmosphere containing gases which will deposit carbon
atoms at the surface of the components. The most important of these gases are the hydrocarbons
methane CH4, and propane, C3H8.
They should be of high purity in order to avoid the deposit of oily soot which impedes carburising. To
facilitate better gas circulation and hence, greater uniformity of treatment the hydrocarbon is mixed
with a "carrier" gas. This is generally an "endothermic" type of atmosphere made in a generator and
consisting of a mixture containing mainly nitrogen, hydrogen and carbon monoxide.
The relative proportions of hydrocarbon and carrier are adjusted to give the desired carburizing rate.
Thus, the concentration gradient of carbon in the surface can be "flattened" by prolonged treatment in a
less rich carburizing atmosphere. Control of this type is possible only with gaseous media.
Gas-carburizing is becoming increasingly popular, particularly for the mass production of thin cases. Not
only is it a neater and cleaner process but the necessary plant is more compact for a given output.
Moreover, the carbon of the surface layers can be controlled more accurately and easily with thickness
of about 0.25 1.0 mm.
Heat treatment after Carburizing
If carburizing has been correctly carried out, the core will still be of low carbon content (0.1 0.2%
carbon), whilst the case should have a maximum carbon content of 0.83% carbon (the eutectoid
composition),
as shown: A Indicates the temperature of treatment for the core, and B the temperature of treatment
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for the case.


Considerable gain growth occurs in the material during a
carburizing treatment; therefore a three stage of heat
treatment must be given to the carburized parts to
produce the desired final properties. This heat treatment
involves:
a) Refining the core: first heat-treated with the object of
refining the grain of the core, and consequently
toughening it. This is effected by heating it to just above its
upper critical temperature (about 870 C for the core)
when the coarse ferrite-pearlite structure will be replaced
by refined austenite crystals. The component is then
water-quenched, so that a fine ferrite-martensite structure
is obtained. The core-refining temperature of 870 C is,
however, still high above the upper critical temperature
for the case, so that, at the quenching temperature, the
case may consist of large austenite grains.
Fig.: Heat-treatment after carburizing
On quenching these will result in the formation of coarse brittle martensite. Further treatment of the
case is therefore necessary.
b) Refining the case: The component is now heated to about 760 C, so that the coarse martensite of
the case changes to fine-grained austenite. Quenching then gives a fine-grained martensite in the case.
At the same time the martensite produced in the core by the initial quench will be tempered somewhat,
and much will be reconverted into fine-grained austenite embedded in the ferrite matrix (point C in
Figure). The second quench will produce a structure in the core consisting of martensite particles
embedded in a matrix of ferrite grains surrounded by bainite. The amount of martensite in the core is
reduced if the component is heated quickly through the range 650-760 C and then quenched without
soaking. This produces a core structure consisting largely of ferrite and bainite, and having increased
toughness and shock-resistance.
c) Tempering: The component is tempered at about 200 220 C to relieve any quenching strains
present in the case.
CARBONITRIDING
This is a surface-hardening process which makes use of a mixture of carburizing gases and ammonia. It is
sometimes known as "dry cyaniding" a reference to the fact that a mixed carbide-nitride case is
produced as in the ordinary liquid cyanide process. Carbonitriding is a modified form of carburizing and
is not a form of nitriding. The modification in carbonitriding consists of adding ammonia (NH3) to the
carburizing gas so that nitrogen diffuses in the steel case along with carbon. Carbonitriding is usually
carried out at a lower temperature and for a shorter time than gas carburizing, and so a thinner case is
usually produced than by carburizing. The relative proportions of carbon and nitrogen in the case can be
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varied by controlling the ratio of ammonia to hydrocarbons in the treatment atmosphere.


Applications: Carbonitriding is principally used to produce a hard, wear-resistant case in steels, normally
from 0.075 to 0.75 mm thick. Nitrogen increases the hardenability of steel, and so a carbonitrided case
has higher hardenability than a carburized case on the same steel. Maximum hardness and less
distortion can be attained by carbonitriding since less drastic oil quenching than for carburizing can be
used.
NITRIDING
The process is used to put a hard, wear-resistant coating on components made from special alloy steels,
for example, drill bushes. The alloy steels used for this process contain either 1.0% alluminium, or traces
of molybdenum, chromium and vanadium. Nitrogen gas is absorbed into the surface of the metal to
form very hard nitrides. Nitriding is a case-hardening process in which nitrogen in the atomic (N) form is
introduced into the surface of certain grades of steels while they are in the ferritic (BCC) condition.
Generally, it involves placing steel in ammonia gas chamber at 500 6500C for a specified period
upwards of 40 hours. At this temperature the ammonia gas breaks down and the atomic nitrogen is
readily absorbed into the surface of the steel. This allows NH4 to dissociate and N diffuses into the steel
surface. Nitrides forms are extremely hard. The treatment temperature is usually in the 495 to 595C
range for periods of 1 to 100hours depending on the type of steel being treated and the depth of case
desired. Under these conditions, nitrides form at or near the surface of steels, the formation of alloy
nitrides at the nitriding temperature provides the hardening effect.. The case is applied to the finished
component. No subsequent grinding is possible since the case is only a few micrometers thick. However,
this is no disadvantage since the process does not affect the surface finish of the component and the
process temperature is too low to cause distortion.
The principal reasons for surface nitriding steels are: To provide a high surface hardness; To increase
wear resistance and antigalling properties; To increase fatigue life; To provide a surface that is heatresistant up to the nitriding temperature
Since nitriding does not involve heating the steel to austenitic temperatures and subsequent quenching
to form martensite, nitriding can be carried out at comparatively low temperatures and thus produce
less distortion and deformation of the workpiece than carburizing or conventional quenching and
tempering. Volume changes during nitriding are thus relatively small since there is no austenitic-ferritic
transformation.
Some of the advantages of nitriding are:
- Carking and distortion are eliminated since the processing temperature is relatively low and
there is no subsequent quenching.
- Surface hardnesses as high as 1150 HD are obtainable with 'Nitralloy' steels.
- Corrosion resistance of the steel is improved.
- The treated components retain their hardness up to 5000C compared with the 2200C for case151

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hardened plain carbon and low alloy steels.


- Resistance to fatigue is good.
- The process is cheap when large number of components is to be treated.
As disadvantage of nitriding is more expensive than that with casehardening, so that the process is
economical only when large number of components are to be treated.
INDUCTION-HARDENING
Used for C>0.35%, these processes are similar in principle to flame-hardening, except that the
component is held stationary- whilst the whole of its surface is heated simultaneously by electromagnetic induction (placing the part in a magnetic field generated by high-frequency alternating current
passing through a water-cooled copper induction coil). The rapidly alternating magnetic field produced
within the coil induces current flow within the steel surface. The induced current i within the steel then
produces heat according to the relationship heat = i2R, where R is the electrical resistance of the steel.
The component is surrounded by an inductor block through
which a high-frequency current in the region of 2ooo Hz, passes
i.e. Eddy currents induced in the steel surface causing I2R
heating of the surface within a very short time thus, Induction
heating requires close control of time and temperature of
heating. This raises the temperature of the surface layer to
above its upper critical in a few seconds. The principle of
induction hardening of a steel surface is to rapidly heat the
surface of a steel workpiece into the austenitic condition and
then quickly quench the piece so that its surface is transformed
into a hard martensitic case (The surface is quenched by
pressure jets of water which pass through holes in the inductor
block) for parts/sections that attained heating above A3.
Fig.: Surface hardening with induction hardening.
Thus, as in flame-hardening, the induction processes make use of the existing carbon content (which
must be above 0-4%), whilst in both case-hardening and nitriding an alteration in the composition of the
surges layer of the steel takes place. Since no change in composition is involved in the workpiece, the
steel must be selected for case and core properties. Thus, for surface induction hardening steels usually
contain 0.4 to 0.75% carbon, and the core properties must be produced by heat treatment before surface
induction hardening.
It has the following principal advantages: increased wear resistance and improved fatigue strength, Very
short process time, freedom from scaling and oxidation (clean work), No risks for distortion when
quenching, process is automated, low energy cost.

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Applications: in general it is used when large numbers of symmetrically shaped parts are to be surfacehardened. using induction heating surface hardening are crankshafts, camshafts, axle shafts, gears,
cams, and valve seats.
FLAME HARDENING
Localized surface hardening (oxy-acetylene torch for local heating and quenching of part that need to be
surface hardened) can also be achieved in medium- and high-carbon steels and some cast irons by rapid
local heating and quenching, used for C>0.35%.. The principle of flame hardening a steel workpiece is to
quickly heat its surface to the austenitic temperature range and then rapidly quench the workpiece to
produce a martensitic structure on the surface layer. In flame hardening the surface layer of steel is
quickly heated by the direct impingement of a high-temperature flame by using, for example, an
oxyacetylene or oxyhydrogen torch.
The quenching action after heating is accomplished by a combination of heat extraction by the cold
metal beneath the case and by an external quenching medium. Steels for flame hardening usually
contain 0.4 to 0.75% carbon, and since there is no change in composition, the steel to be flamehardened is selected for both case and core properties. Since the core structure is not affected by the
surface treatment, the core properties must be developed by proper heat treatment before the surface
treatment. In general, a hard surface layer of martensite is produced and a softer inner core that has a
ferrite-pearlite structure.
A carriage moves over the work piece so that the
surface is rapidly heated by an oxy-acetylene or an
oxy-propane flame. The same carriage carries the
water-quenching spray. Thus the surface of the
work piece is heated and quenched before its core
can rise to the hardening temperature. This
process is often used for hardening the slideways
of machine tools, such as gears, spindles and pins,
that are confidently treated by this process, since
they can be spun between centers.

Fig.: The principle of flame hardening for Surface hardening with flame hardening (Shorter process).
It has the following advantages: Only desired areas are affected, short time process, even very large
pieces can be hardened.
Applications: Flame hardening is applied to a wide diversity of ferrous workpieces. Some examples are:
(i) Parts so large as to make conventional furnace heating impractical such as large gears, dies, and rolls
and (ii) Small sections or areas of a part that require surface hardening such as the ends of valve stems
and push rods and the wearing surfaces of cams and levers.
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LASER HARDENING
In laser hardening the surface of the steel workpiece is heated into the austenitic region without a
change in composition. The heat source is a laser which generates an intense localized heating. The
workpiece itself acts as a cooling sink, and no external quenching medium is required. Laser heating is
usually used to produce a shallow layer of martensite on the steel workpiece.
Commonly, a traveling laser beam at a controlled speed moves across the surface to be hardened. The
case depth is usually shallower than those produced by induction and flame hardening.
Advantages of laser hardening include the ability to harden relatively small areas in complex shapes, e.g.,
small bores. A disadvantage of the process is the cost of the laser.

HEAT TREATMENT OF STEELS


Plain carbon steels and alloy steels are among the relatively few engineering materials which can be
usefully heat treated in order to vary their mechanical properties. The other main group is the heattreatable aluminium alloys. Steels can be heat treated because of the structural changes that can take
place within solid iron-carbon alloys.
In all the HT processes
(Annealing, Normalizing,
Hardening, Tempering) the steel
is heated slowly to the
appropriate temperature for its
carbon content and then cooled.
It is the rate of cooling
which determines the ultimate
structure and properties that
the steel will have, providing
that the initial heating has been
slow enough for the steel to
have reached phase equilibrium
at its process temperature

Fig.: Heat-treatment temperature Ranges of Classes of Carbon Steels in Relation to the Equilibrium
Diagram.
Surface Hardening comprises of thermochemical treatments to harden surface of part (carbon,
nitrogen). It is also called case hardening. Case Hardening - create C- or N- rich outer layer in steels by
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atomic diffusion from the surface. Makes harder outer layer and also introduces compressive stresses.
May or may not require quenching. Interior remains tough and strong
Reasons to Surface Harden:
Increase wear resistance
Increase surface strength for load carrying (crush resistance)
Induce suitable residual and compressive stresses
Improve fatigue life
Impact resistance
Methods to Surface Harden
Heat Treatment: Induction, Flame, Laser, Light, Electron beam
Case Hardening: Carburizing; Cyaniding, Carbonitriding, Nitriding
Heat Treatment
Procedure (typically for medium to high carbon steels)
- Heat surface to austenize (interior stays below austenite transition temperature)
- Cool to form surface martensite ( Interior is not modified and Surface is in compression)
- Subsequent tempering typically done
Characteristics
Hardened depth depends on Frequency (for induction heating effects the depth of the skin. E.g.
1,000Hz 4.5-9mm, 1,000,000 Hz 0.25-0.8mm
Heat flow (flame)
Surface Rc 50-60 (martensite or tempered martensite)
Interior Rc 10-20 (pearlite-ferrite)
Case Hardening
Reasons: Easy to control depths; Good for complicated parts; Mass production compatible; Can use
with low carbon steels (cheaper and tougher)
Steel Crystal Structures:

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Ferrite BCC iron w/ carbon in solid


solution (soft, ductile, magnetic)
Austenite FCC iron with carbon in
solid solution (soft, moderate
strength, non-magnetic)
Cementite Compound of carbon
and iron FE3C (Hard and brittle)
Pearlite alternate layers of ferrite
and cementite.
Martensite iron carbon w/ body
centered tetragonal result of heat
treat and quench
Heat treatment: Ferrite then
austenite then martensite
Fig.: Equilibrium microstructure of iron-carbon alloys at room remperature (about x500)

Fig.: Microstructures of annealed carbon steel. (a) About 0.2%C, (b) about 0.6%C. the light areas are
ferrite and the dark are pearlite.

Fig.: Microstructures of carbon steels (a) ferrite: pure iron and low carbon steel(x100). Austenite has
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about the same microscopic appearance. (b) Pearlite: an annealed 0.8%C steel is 100% pearlite. The dark
lines are Fe3C; the light areas are ferrite (x1300). (c) Martensite: quench-hardened steels (x500).
Heat Treatment of Steels
Heat Treatment Methods
Furnaces
Fuel-fired - parts exposed to combustion products
Electric
Batch or continuous
Vacuum - prevents oxidation of surface
Salt bath
Fluidized bed - particles suspended by gas flow - improves heat transfer
Flame; Electron or laser beam heating, Induction heating, High-frequency (HF) resistance heating

Fig.: Induction heating and High-frequency (HF) resistance heating

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- Steel = 0.06% to 1.0% carbon


-Must have a carbon content of
at least .6% (ideally) to heat
treat.
-Must heat to austenitic
temperature range.
- Must rapid quench to prevent
formation
of
equilibrium
products.
-Basically crystal structure
changes from BCC to FCC at
high Temp.
-The FCC can hold more carbon
in solution and on rapid cooling
the crystal structure wants to
return to its BCC structure. It
cannot due to trapped carbon
atoms. The net result is a
distorted crystal structure
called body centered tetragonal
called martensite.

Martensite is a metastable structure, and


it decomposes when reheated.
In lath martensites of low-carbon plaincarbon steels there is a high dislocation
density, and these dislocations provide
lower energy sites for carbon atoms than
there regular interstitial positions. This
process can take place between 20 and
200C.
The Ms stands for Martensite Start Temperature and the Mf stands for Martensite Finished
Temperature. If a sample is cooled fast enough to prevent the diffusive transformation from taking
place, then martensite will be formed

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Fig.: The Complete TTT Diagram for Pure Fe.

Fig.: Martensite Transformation in Steels


The Martensite in Steel is Not Cubic: The crystal structure of 0.8% Carbon martensite is shown below.
To make room for the carbon atoms the lattice stretches along on crystal direction. This produces a face
centered tetragonal unit cell. Note that only a small proportion of the labeled sites actually contains a
carbon atom. (Reminder: a for BCC iron =0.288nm)

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The Carbon atoms fit into interstitial spaces in the FCC Austenite structure schematically shown below.
Note the distortion of the Fe atoms [0.258-nm diameter] around the Carbon atoms [0.154-nm diameter]
since the voids are 0.104-nm diameter.

Fig.: Fe-C Interstitial Solid Solution in Austenite


The Carbon atoms cannot fit into interstitial spaces in the BCC ferrite structure like they can in the FCC
Austenite and produce a BCT ( schematically shown below). Note in the BCT the Carbon atoms force the
unit cell to be elongated in the c-direction. The largest interstitial void in BCC iron has a diameter of
0.072-nm.

Fig.: Fe-C Interstitial Solid Solution in Ferrite & Martensite


Interpretation of the Iron-Iron Carbide Phase Transformations on the T-T-T Diagram

Fig.: Fe-Fe3C T-T-T diagram

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Fig.: Isothermal Transformation Experiment


The time-temperature transformation curves correspond to the start and finish of transformations
which extend into the range of temperatures where austenite transforms to pearlite. Above 550C,
austenite transforms completely to pearlite. Below 550C, both pearlite and bainite are formed and
below 450C, only bainite is formed. The horizontal line C-D that runs between the two curves marks the
beginning and end of isothermal transformations. The dashed line that runs parallel to the solid line
curves represents the time to transform half the austenite to pearlite. Below we have listed some simple
examples as an exercise at other temperatures that result in different phase transformations and hence
different microstructures.
Example: Describe what transformations happen in: (a) Path 1; (b) Path 2; (c) Path 3; (d) Path 4

Sol: (a) The specimen is cooled rapidly to 433 K and left for 20 minutes. The cooling rate is too rapid for
pearlite to form at higher temperatures; therefore, the steel remains in the austenitic phase until the M s
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Temperature is passed, where martensite begins to form. Since 433 K is the temperature at which half
of the austenite transforms to martensite, the direct quench converts 50% of the structure to
martensite. Holding at 433 K forms only a small quantity of additional martensite, so the structure can
be assumed to be half martensite and half retained austenite.
(b)The specimen is held at 523 K for 100 seconds, which is not long enough to form bainite. Therefore,
the second quench from 523 K to room temperature develops a martensitic structure.
(c) An isothermal hold at 573 K for 500 seconds produces a half-bainite and half-austenite structure.
Cooling quickly would result in a final structure of martensite and bainite.
(d) Austenite converts completely to fine pearlite after eight seconds at 873 K. This phase is stable and
will not be changed on holding for 100,000 seconds at 873 K. The final structure, when cooled, is fine
pearlite.
HEAT TREATMENTS OF STEELS

HARDENING

Direct hardening
Austenitize and
quenching

Diffusion hardening
Carburize (diffuse C)
Nitride (diffuse N)
Boronize (diffuse B)

Selective
Special species (Diffuse
Austenitize and
V, Si, etc.
quenching: Flame;
Carbonitriding (Diffuse C+N)
Induction; Laser;
Ferritic nitrocarburizing
Electron beam
(Diffuse C+N)

SOFTENING

CONDITIONING

Recrystallization

Stress relieving

Annealing: Process;
Full; Spheroidizing;
Normalizing

Spring aging

Tempering:
Austempering;
Martempering

Steam treating
Cryogenic
treatment

Heating for hot working

DIRECT HARDENING
When a piece of steel, containing sufficient carbon, is cooled rapidly from above its upper critical
temperature it becomes considerably harder than it would be if allowed to cool slowly.
This involves rapidly quenching the steel, from a high temperature into oil or water. Hypereutectoid
steels are heated to (30- 500C) above the upper critical temperature prior to quenching. It is possible
that some cementite grain boundaries.
Consequently, hypereutectoid steels are hardened by quenching from (30- 50 C) above the lower critical
temperature. At this temperature the structure because one of spheroidal cementite particles in an
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austenite matrix.
The degree of hardness produced can vary, and is dependent upon such factors as the initial quenching
temperature; the size of the work; the constitution, properties and temperature of the quenching
medium; and the degree of agitation and final temperature of the quenching medium.
Austenitizing and quench: Heat to austenite
range. Want to be close to transformation
temperature to get fine grain structure
Austenitizing again taking a steel with .6%
carbon or greater and heating to the
austenite region.
Rapid quench to trap the carbon in the crystal
structure called martensite (BCT)
Quench requirements determined from
isothermal transformation diagram (IT
diagram).
Get Through Hardness

Fig.: hardening temperature range shown on Fe-C diagram


To harden apiece of steel, it must be heated then quenched in some media which will produce in it the
desired rate of cooling . the medium used will depend upon the composition of the steel and the
ultimate properties required. The quenching medium is chosen according to the rate at which it is
desired to cool the steel. The following list of media is arranged in order of quenching speeds: 5 %
Caustic soda, 5 20 % Brine, Cold water, Warm water, Mineral oil.

Fig.: Typical Time-Temperature transformation diagram (IT)


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For this particular steel want to cool from about 1400 F to <400 F in about 1 second!
Quenching: Depending on how fast steel must be quenched (from IT diagram), the heat treater will
determine type of quenching required: Water (most severe); Oil, Molten Salt, Gas/ Air (least severe),
Many phases in between. Ex: add water/polymer to water reduces quench time, Adding 10% sodium
hydroxide or salt will have twice the cooling rate.
Selective Hardening:
Same requirements as austenitizing: Must have sufficient carbon levels (>0.4%), Heat to austenite region
and quench
Why do?
- When only desire a select region to be hardened: Knives, gears, etc.
- Object to big to heat in furnace! Large casting w/ wear surface
Types: Flame hardening, induction hardening, laser beam hardening

Fig.: Typical flame-hardening systems

Fig.: frame-hardening profiles (white areas) for typical mechanical components

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Fig.: Induction hardening


DIFFUSION HARDENING (aka CASE HARDENING):
Why do?
Carbon content to low to through harden with previous processes.
Desire hardness only in select area
More controlled versus flame hardening and induction hardening.
Can get VERY hard local areas (i.e. HRC of 60 or greater)
Interstitial diffusion when tiny solute atoms diffuse into spaces of host atoms
Substitutional diffusion when diffusion atoms to big to occupy interstitial sites then must
occupy vacancies
Diffusion concepts:
Atomic Vibrations: Heat causes atoms to vibrate. Vibration amplitude increases with temperature.
Melting occurs when vibrations are sufficient to rupture bonds. Vibrational frequency ~ 1013 Hz. Average
atomic / electronic energy due to thermal excitation is of order kT [with a distribution around this
average energy, P(E) ~ exp(-E/kT)] k : Boltzmanns constant, (1.38x10-23J/K or 8.62 x 10-5 eV/K), T:
Absolute temperature (Kelvin)
(a) Model:

The flux of diffusing atoms, J =

] , is used to

quantify how fast diffusion occurs. The flux is defined as either in


number of atoms diffusing through unit area and per unit time (e.g.,
atoms/m2-second) or in terms of the mass flux - mass of atoms
diffusing through unit area per unit time, (e.g., kg/m2-second).

Steady state diffusion: the diffusion flux does not change with time.
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Concentration profile: concentration of atoms/molecules of interest as function of position in the


sample.
Concentration gradient: dC/dx (Kg.m-4): the slope at a particular point on concentration profile.

Ficks first law: the diffusion flux along direction x is


proportional to the concentration gradient
where D is the diffusion coefficient
The concentration gradient is often called the driving
force in diffusion (but it is not a force in the mechanistic
sense). The minus sign in the equation means that
diffusion is down the concentration gradient.
Flicks law (Diffusion Temperature Dependence)

where J: Flux of atoms (atoms/time/area);

D: Diffusion coefficient (area/time) is the measure of mobility of diffusing species.; dc/dx: concentration

gradient (c: atoms/volume; x:distance); Diffusion coefficient:


2

constant for a material (temperature-independent preexponential (m /s));

; where

=a diffusion

: Activation energy for

process to occur;
depends on material system it is the activation energy for diffusion (J/mol or
eV/atom), R is the gas constant (8.31 J/mol-K or 8.6210-5 eV/atom-K) and T is absolute temperature (k).
The above equation can be rewritten as
( )
( )
The activation energy Qd and preexponential
D0, therefore, can be estimated by plotting
lnD versus 1/T or logD versus 1/T. Such plots
are Arrhenius plots.
Fig.: Plot of the logarithm of the diffusion coefficient versus the 1/T for Cu in Au.
(b) How diffusion occurs
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Fig.: Basic concepts for diffusion processes


Diffusion is material transport by atomic
motion. Inhomogeneous materials can
become homogeneous by diffusion. For
an active diffusion to occur, the
temperature should be high enough to
overcome energy barriers to atomic
motion.

Interdiffusion and Self-diffusion


Interdiffusion occurs in response to a concentration gradient (more rigorously, to a gradient in chemical
potential)

To move from lattice site to lattice site, atoms need energy to break bonds with neighbors, and to cause
the necessary lattice distortions during motion from site to another. This energy comes from atomic
vibrations (Eav ~ kT)

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Fig.: Atomic migration by a mechanism of vacancy migration (Before and after). Materials flow (the
atom) is opposite the vacancy flow direction.
Interstitial diffusion (depends on temperature). This is generally faster than vacancy diffusion because
there are many more interstitial sites than vacancy sites to jump to. Requires small impurity atoms (e.g.
C, H, O) to fit into interstices in host.

Fig.: Interstitial diffusion


Self diffusion (motion of atoms within a pure host) also occurs. Predominantly vacancy in nature difficult
for atoms to fit into interstitial sites because of size.
(c) Where diffusion applies
Solute
Host
Carburizing
C
Low-carbon steels
Nitriding
N
Nitriding steels
Carbonitriding
C+N
Low-carbon steels
Boronizing
B
Low-carbon steels
Chromizing
Cr
Low- and high-carbon steels
Carbonotriding - use both carbon and nitrogen. Chroming - pack or dip in chromium-rich material - adds
heat and wear resistance. Boronizing - improves abrasion resistance, coefficient of friction
Requirements: High temp (> 900 F); Host metal must have low concentration of the diffusing species;
must be atomic suitability between diffusing species and host metal
Most Common Types:
1. Carburizing: Pack carburizing: Firstly, low carbon steel is heated at 900-9500C for a specified time in
an environment with carbon concentration and carbon diffuses in steel when in gaseous (atomic) form.
Secondly, after carburizing for time t, the material work is taken out of the furnace and left to cool in air
then heated to 830-8600C, then quench in water (for plain carbon steels) or in air (for alloy steels).
Pack carburizing is the most common (packing parts in charcoal or coke - makes thick layer (0.025 0.150 in)
Part surrounded by charcoal treated with activating chemical then heated to austenite temperature.
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Charcoal forms CO2 gas which reacts with excess carbon in charcoal to form CO. CO reacts with lowcarbon steel surface to form atomic carbon. The atomic carbon diffuses into the surface. Must then be
quenched to get hardness

Fig.: Pack carburizing and effect of carburizing temperature on case depth

Fig.: Microhardness Through Case zone: Determination of carburized or carbonitrided case depth by
microhardness survey

Fig.: Microstructure through carburized surface. 0.20%C-steel pack carburized at 17000F for 6 hours
and furnace-cooled. Etched in 2% initial (30X)
Other rare carburizing methods:
- Gas carburizing - use of propane or other gas in a closed furnace - makes thin layer (0.005 - 0.030 in)
- Liquid carburizing - molten salt bath containing sodium cyanide, barium chloride - thickness between
other two methods

2. Nitriding: Nitrogen diffused into surface of special alloy steels (aluminum or chromium) being treated.
Nitrogen reacts with steel to form very hard iron and alloy nitrogen compounds. Nitride compounds
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precipitate out. Process does not require quenching big advantage. The case can include a white layer
which can be brittle disadvantage. It is More expensive than carburizing. Reduction process:

Types: Gas nitriding - heat in ammonia and Liquid nitriding (Carbonitriding) - dip in molten cyanide bath
(Cyaniding)

Fig.: Schematic of gas nitriding system

Fig.: Hardness of nitrided case


SOFTENING AND CONDITIONING
1. Recrystallization: Done often with cold working processes. Limit to how much steel can be cold
worked before it becomes too brittle. This process heats steel up so grains return to their original size
prior to subsequent cold working processes. Also done to refine coarse grains
2. Annealing: All annealing processes are concerned with rendering steel soft and ductile, hence
prepare it for additional processing such as cold forming/working or machining . If already cold worked allows recrystallization.
What does it do? Answer: Reduce hardness, Remove residual stress (stress relief), Improve toughness,
Restore ductility, Refine grain size
Process Steps:
1. Heat material into the austenite region (i.e. above 1600F) rule of thumb: hold steel for
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one hour for each one inch of thickness


2. Slowly furnace cool the steel DO NOT QUENCH
3. Key slow cooling allows the C to precipitate out so resulting structure is coarse pearlite
with excess ferrite
4. After annealing steel is quite soft and ductile
Annealing versus Austenitizing:
a) End result: One softens and the other hardens!
b) Both involve heating steel to austenite region.
c) Only difference is cooling time:
- If fast (quenched) C is looked into the structure = martensite (BCT) = HARD
- If slow C precipitates out leading to coarse pearlite (with excess cementite of ferrite) = SOFT

Fig.: Annealing temperature for plain carbon steel .


There are three basic annealing processes:
(i) Stress-relief annealing (at subcritical temperatures): also called 'process annealing' 'interstage
annealing' and subcritical annealing, not heated as high as full anneal. often used for softening cold
worked low carbon (0.4 % carbon content) steel or mild steel. To fully anneal such a steel would involve
heating to a temperature of more than 900C, with consequent high cost. In a mild steel ferrite makes
up about 90 % of the structure, and the recrystallisation temperature of cold worked ferrite is only
about 500C. annealing a cold worked mild steel in the temperature range 550 600 C will result in
complete recrystallisation of ferrite, although the cold worked pearlite will be largely unaffected.
Frequently, however, we must apply a considerable amount of cold-work to mild steels, as, for example,
in the drawing of wire. Stress-relief annealing then becomes necessary to often the metal so that further
drawing operations can be carried out. Such annealing is carried out at about 650 C. Since this
temperature is well above the recrystallisation temperature of 500 C, recrystallisation will be
accelerated so that it will be complete in a matter of minutes on attaining the maximum temperature.
It should be noted that process annealing is a sub-critical operation, that is, it takes place below the
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change and the constituents ferrite and cementite remain present in the structure throughout the
process.
Process annealing is generally carried out in either batch-type or continuous furnaces, usually with an
inert atmosphere of burnt coal gas, though cast-iron annealing "pots" are still used, their lids being luted
on with clay.
(ii) Full annealing for forgings, Large castings and weldments: lower temp (1,000F), slow cooled. It is the
treatment given to produce the softest possible condition in a hypoeutectoid steel. It involves heating
the steel to a temperature within the range 30 50 C above the upper critical temperatures and then
allowing the steel to cool slowly within the furnace. This produces a structure containing coarse pearlite.
This results in the formation of fine grains of austenite that transform into relatively fine grains of ferrite
and pearlite or pearlite and cementite (depending upon the carbon content) as the steel is slowly cooled
to room temperature, usually in the furnace.
Full annealing is an expensive treatment and when it is not absolutely essential for the steel to be in a
very soft condition, but a reasonably soft and ductile material is required, the process known as
normalizing is used instead.
Ferrite, which then begins to precipitate in accordance with the equilibrium diagram, deposits first at
the grain boundaries of the austenite, thus revealing, in the final structure, the size of the original
austenite grains. The remainder of the ferrite is then precipitated along certain crystallographic planes
within the lattice of the austenite. This gives rise to a directional precipitation of the ferrite, as shown in
figure below. and Plate , representing typically what is known as a Widmanstatten structure.

Fig.: The structural effects of heating a steel casting to a temperature just above its upper critical ,
followed by cooling to room temperature.
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This type of structure was first encountered by Widmanstatten in meteorites, which may be expected to
exhibit a coarse structure in view of the extent to which they are overheated during their passage
through the upper atmosphere. .The mesh-like arrangement of ferrite in the Widmanstatten structure
tends to isolate the stronger pearlite into separate patches, so. that strength, and more particularly
toughness, are impaired. The main characteristics of such a structure are, therefore, weakness and
brittleness, and steps must be taken to remove it either by heat-treatment or by mechanical working.
Hot-working will effectively break up this coarse as-cast structure and replace it by a fine-grained
material, but in this instance we are concerned with retaining the actual shape of the casting. Heattreatment must therefore be used to effect the necessary refinement of grain.
This operation need a very specific controlling on the heat temperature of annealing because if any fault
is across, it will make some undesired phases in the steel such as: Over heating, Burning (Excessive over
heating), and Under-qunealing
(iii) Spheroidised annealing at subcritical temperatures. The Spheroidised condition is produced by
annealing the steel at a temperature between 650 and 700 C, just below the lower critical temperature.
During this treatment cementite forms as spheroidal particles in a ferrite matrix, putting the steel into a
soft, but very tough, condition.
Since the temperature involved are sub critical no phase changes take place and spheroidization of the
cementite is purely a surface tension effects. This is referred to as the a spheroidization of pearlitic
cementite

Fig.: The Spheroidization of Pearlitic Cementite.


Normalizing: use when max softness not required and cost savings desired (faster than anneal). Air
cooled vs. furnace cooled.
3. Normalizing
The process resembles full annealing except that, whilst in annealing the cooling rate is deliberately
retarded, in normalizing the cooling rate is accelerated by taking the work from the furnace and allowing
it to cool in free air. Provision must be made for the free circulation of cool air, but draughts must be
avoided.
In the normalizing process, as applied to hyper-eutectoid steels, it can be seen that the steel is heated to
approximately 50 C above the upper critical temperature line. This ensures that the transformation to
fine grain austenite corrects any grain growth or grain distortion that may have occurred previously.
Again, the steel is cooled in free air and the austenite transforms into fine grain pearlite and cementite.
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The fine grain structure resulting from the more rapid cooling associated with normalizing gives
improved strength and toughness to the steel but reduces its ductility and malleability. The increased
hardness and reduced ductility allows a better surface finish to be achieved when machining. (The
excessive softness and ductility of full annealing leads to local tearing of the machined surface.)
The type of structure obtained by normalizing will depend largely upon the thickness of cross-section, as
this will affect the rate of cooling. Thin sections will give a much finer grain than thick sections, the latter
often differing little in structure from an annealed section.
Although highly successful, this procedure tied up an excessive amount of working capital and space and
nowadays heat treatment is preferred as the work in progress is turned round more quickly.
4. Tempering: A quench-hardened plain carbon steel is hard, brittle and hardening stresses are present.
In such a condition it is of little practical use and it has to be reheated, or tempered, to relieve the
stresses and reduce the brittleness. This temperature will remove internal stress setup during quenching,
remove some, or all, of the hardness, and increase the toughness of the material.
Almost always done following heat treat as part of the austenitizing process. Because of lack of
adequate toughness and ductility after heat treat, high carbon martensite is not a useful material
despite its great strength (too brittle). Tempering causes the transformation of martensite into less
brittle structures. Unfortunately, any increase in toughness is accompanied by some decrease in
hardness. Tempering always tends to transform the unstable martensite back into the stable pearlite of
the equilibrium transformations. Thus it imparts a desired amount of toughness and ductility (at the
expense of strength)
Typical HT steps:
- Austenize: Heat into stable single phase region and HOLD for uniform chemistry single phase
austenite.
- Quench: Rapid cool crystal changes from Austenite FCC to Martensite BCT which is hard but
brittle.
- Temper: A controlled reheats (BELOW AUSTENITE REGION). The material moves toward the
formation of a stable two phase structure tougher but weaker.
- Quench: The properties are then frozen in by dropping temperature to stop further diffusion
Tempering temperatures below 2000C only relieve the hardening stresses, but above 2200C the hard,
brittle martensite starts to transform into a fine pearlitic structure called secondary troostite (or just
'troostite'). Troostite is much tougher although somewhat less hard than martensite and is the structure
to be found in most carbon-steel cutting tools.
Tempering above 4000C causes any cementite particles present to "ball-up" giving a structure called
sorbite. This is tougher and more ductile than troostite and is the structure used in components
subjected to shock loads and where a lower order of hardness can be tolerated, for example springs. It is
normal to quench the steel once the tempering For most steels, cooling form the tempering
temperature may be either cooling in air, or quenching in oil or water. Some alloy steels, however, may
be become embrittled if slowly cooled temperature has been reached. from the tempering temperature,
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and these steels have to be quenched.

Fig.: Effect of tempering on the properties of a quench-hardened carbon steel (1040-1060)


Microstructural changes in martensite with tempering: For martensitic plain-carbon steels with more
than 0.2% carbon tempering produces Cementite, Fe3C.
The shapes are different at different temperatures. The important point is that the Fe matrix returns to
its BCC form found in Ferrite. The electron micrographs below show the microstructure for two
treatments.

5950C (11000F) 1hr, 33Rc


6750C (12500F), 12hr, 20Rc
Fig.: Electron micrographs of tempered martensite (x11000). Each of these is eutectoid steel which
was previously quenched to maximum hardness (65Rc).

Fig.: Martempering and austempering


Martempering: Less volume changes due to transformation (reduced risk of cracking, wrapping).
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Austempering: Bainite structure is tougher than martensite.

Fig.: Heat treating Processes with their thermal cycles

DEFFECTS IN HARDENED STEELS


1. Low hardness due to underheating
2. Formation of soft spots due to underheating or inhomogeneous initial structure
3. Increase brittleness due to hardening from an excessively high temperature.
4. Oxidation of the surface due to uncontrolled surface atmosphere.
5. Deformations, warpage and cracks due to improper method for quenching, improper manner of
heating, etc.

1.1.2 NON-FERROUS METALS


They do not contain Fe as their chief constituents. Al, Cu, Ag, Au are good conductors of electricity. Ag is
most malleable, Au is most ductile and Chromium is corrosion resistant. Zinc is used in metal plating, Tin
is used to make bushes and Nickel imparts strength and creep resistance.
A metal alloy is a combination of two or more metals. They possess properties quite different from
those of their constituent metals. They are found under ferrous and non ferrous alloys depending on
their base metal.
5.5 NON FERROUS METALS AND THEIR ALLOYS
There are many metals that do not have iron as their base metal. The term non-ferrous metals refers to
the thirty-eight metals other than iron that are known to man. They offer specific properties or
combinations of properties that make them ideal for tasks where ferrous metals are not suitable. The
most commonly used ones are: Alluminium, copper, lead, silver, tin, zinc, chromium, cobalt, manganese,
molybdenum and nickel.
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Two of the most important are Alluminium and copper since they not only form the bases of many
important alloys, but they are widely used in their own right as pure metals.
5.5.1 ALLUMINIUM AND ITS ALLOYS
Pure Alluminium is a weak, ductile material with a low density. Its electrical conductivity is second only
to copper for conductors of the same mass. Its thermal conductivity and light reflectivity are quite high.
It is also highly resistant to corrosion against many types of attack which are harmful to other metals;
this is due to the formation of a very adherent homogeneous and transparent film on a fleshly cut
surface caused by the high affinity of Alluminium to oxygen. This oxide layer is amphoteric (can behave
as either basic or acidic oxide). Alluminium is an FCC material therefore it has numerous (12) slip
systems, leading to good ductility.
The wear resistance of Alluminium, as suspected from its low yield stress and hardness, is not good. The
fatigue strength is not high. Its low modulus of elasticity must be considered when cold working due to
the springback when unloaded.
Because of its creep strength that limits its use to fairly low temperatures (1750C recommended) and the
low strength that makes it of little use as a structural material, aluminum alloys are preferred.
Effects of alloying elements in alluminium
-

They provide better casting characteristics (fluidity and gas tightness) in casted alloys: silicon
They improve mechanical properties: copper, nickel. Copper raises also strength at high
temperatures (use in piston castings and heat exchangers). The highest strength alloy of
Alluminium is the one containing 5-6% zinc with slammer amount of magnesium and copper.
- They improve corrosion resistance: Magnesium, manganese or small amounts of chromium
- They improve machineability: Lead and bismuth
Aluminum and its alloys are produced and used in many shapes and forms. The common forms are
castings, sheet, plate, bar, rod, channels, and forgings. Aluminum alloys have many desirable qualities.
They are lighter than most other metals and do not rust or corrode under most conditions. Aluminum
can be cast-forged, machined, and welded easily.

5.5.2 COPPER AND ITS ALLOYS


Copper is a reddish metal, very ductile and malleable, and has high electrical and thermal conductivity
(only exceeded by those of silver). Their FCC structure contributes to their high ductility and formability
so it is drawn into rods, wires and tubes. It can also be forged, cast, cold worked, welded, but its
machinability is only fair. Like alluminium, it prevents oxidation by forming oxide film. Their coloration is
used for architectural appearance.

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The principal use of commercially pure copper is in the electrical industry where it is made into wire or
other such conductors in radiators and heat exchangers. It is also used in the manufacture of nonferrous
alloys such as brass, bronze, and monel metal. Typical copper products are sheet roofing, cartridge
cases, bushings, wire, bearings, and statues.
Effects of alloying elements in copper.
Zinc, tin, alluminium and silicon are among the most frequently used solid solution hardeners for
copper.
-

Zinc increases strength. Muntz metal is an alloy containing 40%zinc. The alloys of copper and
zinc are known as brasses (used in cartridge casings, musical instruments, etc). They are more
susceptible to stress and erosion corrosion and not more resistant compared to pure copper.
Tin: improves hardness and strength of copper (>10% tin impairs ductility). It has a high cost.
The bronzes are copper alloys involving elements such as tin, alluminium, silicon and nickel.
They have a high degree of corrosion resistance. Tin-bronze alloys are made up by copper and
tin together with a deoxidizer to prevent tin oxidation during casting or hot working which
would result in weak, scratchy bronze. Two deoxidizers are commonly used:
Phosphorus in the phosphor-bronze alloys
Zinc in the gunmetal alloys
Brass and bronze: Brass, an alloy of copper and zinc (60 to 68 percent copper and 32 to 40
percent zinc), has a low melting point and high heat conductivity. There are several types of
brass such as naval, red, admiralty, yellow, and commercial. All differ in copper and zinc content.
All may be alloyed with other elements such as lead, tin, manganese, or iron and all have good
machinability and can be welded. Bronze is an alloy of copper and tin and may contain lead,
zinc, nickel, manganese, or phosphorous. It has high strength, is rust or corrosion resistant, has
good machinability, and can be welded.

Alluminium: the behavior of the copper alloys containing increasing amounts of alluminium is
similar to that of tin alloys. Alluminium bronzes are more expensive than tin-bronzes but more
corrosion resistant at high temperatures due to the aluminum oxide film that forms on its
surface. They are also more ductile and can be cold worked into tubes for boilers and
condensers in steam and chemical plant.
- Nickel: imparts a white color to copper, raises the hardness of copper. Constantan is an alloy of
copper with 45%Ni, it is used for resistors and for thermocouples. Cupro-nickel alloys are
relatively expensive copper-based alloys, but their strength, ductility and corrosion resistance
make them highly suitable for applications such as high-duty boiler and condenser tube and
resistance wires.
Monel metal: this contains traces of Fe and manganese, high corrosion resistant at high
temperatures. Used for chemical plant and marine applications

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Nickel silvers: up to 20%zinc which reduces the cost and imparts a silvery appearance when highly
polished. Used for domestic table cutlery as alternative to stainless steel.
Nickel with the super alloys: Inconel (Ni-Cr-Fe); hastelloy (Ni-Mo-Fe-Cr)
-

Silicon: produces effects similar to those of zinc, tin and alluminium when alloyed with copper.
However, limits of solubility are lower, hence embrittlement occur at lower concentrations.
- Tellurium metal, non-metal sulphur and lead (act as lubricant in bearings) increase machinability
to a good surface finish.
5.5.3 MAGNESIUM AND ITS ALLOYS
Magnesium is the lightest of the engineering metals (1.7g/mm3). It is HCP with only 3 slip systems and
characteristic brittleness. Except for ductility, the properties of pure magnesium are superior to those of
pure aluminium. But magnesium does not respond to heat treatment and mechanical working as
alluminium. Magnesium is considered to be generally weaker than steel and alluminium, although some
alloys of magnesium are stronger than alluminium alloys. For that reason, its structure requires
members of greater section thickness in order to be of the same load-carrying capacity. Properties like
wear resistance, fatigue strength, creep strength (low melting temperature 6500C) and corrosion
resistance are poor.
Magnesium alloys are produced and used in many shapes and forms, for example, castings, bars, rods,
tubing, sheets and plates, and forgings. Their inherent strength, light weight, and shock and vibration
resistance are factors which make their use advantageous. The weight for an equal volume of
magnesium is approximately two-thirds of that for aluminum and one-fifth of that for steel. Magnesium
has excellent machining qualities; however, care must be taken when machining because the chips are
highly flammable. Magnesium fires bum so hot that they cannot be extinguished by conventional fire
extinguishers.
Effect of alloying elements in magnesium
Magnesium alloys contain:
Alluminium: produce a precipitation-hardenable alloy in which the precipitate resembles to pearlite of
steel >7%Aluminium. In solid solution, exerts a slightly hardening effect
Zinc: Solid solution hardener and improves corrosion resistance.
Manganese: in small controlled amounts, improves resistance to attack by salt water.
5.5.4 LEAD
Lead is used mainly in the manufacture of electrical equipment such as lead-coated power and
telephone cables and storage batteries. Zinc alloys are used in the manufacture of lead weights,
bearings, gaskets, seals, bullets, and shot.
Many types of chemical compounds are produced from lead. Among these are lead carbonate (paint
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pigment) and tetraethyl lead (antiknock gasoline). Lead is also used for X-ray protection (radiation
shields). Lead has more fields of application than any other metal. It can be cast, cold worked, welded,
and machined. Lead has low strength with heavy weight.
5.5.5 TIN
The major use of tin is in coating steel. It is the best container for preserving perishable food. Tin, in the
form of foil, is often used in wrapping food products. A second major use of tin is as an alloying element.
Tin is alloyed with copper to produce bronze, with lead to produce solder, and with antimony and lead
to form babbitt. Tin can be die cast, cold worked, machined, and soldered; however, it cannot be
welded.
5.5.6 NICKEL
Nickel is used in making alloys of both ferrous and nonferrous metals. Chemical and food processing
equipment, electrical resistance heating elements, ornamental trim, and parts that must withstand
elevated temperatures are all produced from nickel containing metal. Alloyed with chromium, it is used
to make stainless steel. Nickel alloys are readily welded by either gas or arc methods and can be
machined, forged, cast, and easily formed.
5.5.7 COBALT-CHROMIUM-TUNGSTE-NMOLYBDENUM WEAR-RESISTANT ALLOYS
These alloys feature a wear resistance which makes them ideal for metal-cutting operations. Their ability
to retain hardness even at red-heat temperatures also makes them especially useful for cutting tools.
Common cutting tools will lose their edge at high heat, whereas this alloy group is actually tougher at
red heat than it is when cold; as a result, higher speeds and feeds may be used when machining with
tools made with these alloys.
5.5.8 PRECIOUS METALS
These include silver, gold, platinum, palladium, iridium, osmium, rhodium, and ruthenium, with their
alloys. These alloys are produced under technical and legal requirements. Gold alloys used for jewelry
are described in karats. The karat is the content of gold expressed in twenty-fourths. An 18-karat gold
alloy would contain 18/24 gold (75 percent by weight). Other than jewelry, there are many industrial
uses for precious metals.

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Summary
Metal
Aluminium

Density
3
(Kg/m )
2700

Melting point
(C)
660

Cooper

8900

1063

Lead

11300

328

Silver

960

Tin

Properties

Typical uses

Lightest of the commonly used metals. High


electrical and thermal conductivity. Soft and low
tensile strength 93 MPa
Soft. Ductile and low tensile strength 232MPa.
Second only to silver in conductivity. It is much
easier to join by soldering and brazing than
Alluminium. Corrosion resistant
Soft, ductile and very low tensile strength. High
corrosion resistance

The base of many engineering alloys. Light weight electrical conductors

Soft, ductile and very low tensile strength. Highest


electrical conductivity of any metal
Resists corrosion

7300

232

7100

420

Chromium

7500

1890

Cobalt

8900

1495

Manganese

7200

1260

Molybdenum

9550

2620

Heavy, heat resistant metal that alloys readily with


other metals

Nickel

8900

1158

strong, tough corrosion- resistant metal widely used


as an alloying element

Soft, ductile and low tensile strength. Corrosion


resistant
Resists corrosion, raises strength but lowers ductility of
steels. Improves heat-treatment properties
Improves wear-resistance and hot hardness of high
speed steels
High affinity for oxygen and sulphur, soft and ductile

The base of brass and bronze alloys. It is used extensively for electrical
conductors and heat exchangers such as motor car radiators

Electric cable sheaths the base of solder alloys. The grids for accumulator
plates. Lining chemical plant. Added to other metals to make them freecutting
Widely used in electrical and electronic engineering for switch and relay
contacts
coats sheet mild steel to give 'tin plate' Used 1 soft solders One of the bases of
'white metal' bearings An alloying element In bronzes
Sheet extensively to give galvanized iron. The base of die-casting alloys. An
alloying element in brass
Used as an alloying element in high-strength and corrosion resistant steels.
Used for electroplating
Used as an alloying element in super high speed steels and in permanentmagnet alloys
Used to de-oxidize steels and offset the effects of the impurity sulfur. Larger
amounts improve wear resistance
Used as an alloying element in high-strength nickel-chrome steels to Improve
mechanical and heat - treatment properties. It reduces mass effect and
temper -brittleness
Used as an alloying element to improve the strength and mechanical
properties, of steel. Tends to unstabilise the carbon during heat treatment,
and chromium has to be added to counteract this effect in medium and highcarbon steels. Used for electroplating

Table :Uses, properties of non ferrous metallic materials

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HEAT TREATMENT OF NONFERROUS METALS


Two types of heat-treating operations can be performed on nonferrous metals. They are annealing and
solution heat treating.
ANNEALING
Most nonferrous metals can be annealed. The annealing process consists of heating the metal to a
specific temperature, soaking, and cooling to room temperature. The temperature and method of
cooling depend on the type of metal. Annealing is often accomplished after various cold working
operations because many nonferrous metals become hard and brittle after cold working. Also, annealing
is used to remove the effects of solution heat treatment so that machining or working qualities can be
improved.
SOLUTION HEAT TREATMENT
The tensile strength of many nonferrous alloys can be increased by causing the materials within the
alloy to go into a solid solution and then controlling the rate and extent of return to an altered
mechanical mixture. This operation is called solution heat treatment. After an alloy has been heated to a
specified temperature, it is quenched or cooled rapidly, which traps the materials in the solid solution
attained during the heating process. From this point, the process varies greatly depending on the metal.
To be sure the materials in the alloy do not revert to their original configuration after a period of time, a
process of aging or precipitation hardening must follow. In this process the materials in the alloy are
allowed to change or to precipitate out of the solid solution. This process occurs under controlled
conditions so that the resultant grain structure will produce a greater tensile strength in the metal than
in its original condition. Depending on the alloy, this precipitation process can also consist of simply
aging the alloy at room temperature for a specified time and then air-cooling it; this is called artificial
aging. Aluminum alloys can be obtained in various conditions of heat treatment called temper
designations. Figure 2-11, on page 2-9, shows the various temper designations and the process to which
they apply. The term strain-hardened refers to aging or hardening that has been brought about by
coldworking the alloy. Stabilizing refers to a particular aging process that freezes or stops the internal
changes that normally would take place in the alloy at room temperature.
Magnesium alloys can be subjected to all of the nonferrous heat treatments, but the different alloys
within the series require different temperatures and times for the various
processes. Copper alloys are generally hardened by annealing. The nickel alloys can also be annealed
and certain types can be hardened by heat treatment. Likewise, titanium may be annealed (mostly
relieve machining or cold-working stresses) but is not noticeably affected by heat treatment.

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7. ENGINEERING MATERIALS TESTING


7.1 DESTRUCTIVE TESTING
7.1.1 Tensile test: the aim of the tensile test is to determine the strength, stiffness and ductility of a
material. It is a static test in which a specimen is pulled until fracture. The test machine is usually a
hydraulic or screw type device consisting of two cross heads in which the test specimen is held.

Fig.7.1: Proportions of tensile test specimens: (a) Cylindrical, (b) flat


The load applied and the corresponding extension can be plotted in the form of a graph

Fig.7.2: Load extension curve for low-carbon steel.


From A to B the extension is proportional to the applied load. Also, if the applied load is removed the
specimen returns to its original length. Under these relatively lightly loaded conditions the material is
showing elastic properties.
From B to C it can be seen from the graph that the metal suddenly extends with no increase in load. If
the load is removed at this point the metal will not spring back to its original length and it is said to have
taken a permanent set. This is the yield point.

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The yield stress is the stress at the yield point; that is, the load at B divided by the original cross-section
area of the specimen. Usually, a designer works at 50 per cent of this figure to allow for a 'factor of
safety'.
From C to D extension is no longer proportional to the load, and if the load is removed little or no spring
back will occur. Under these relatively greater loads the material is showing plastic properties.
The point D is referred to as the 'ultimate tensile strength' when referred to loadextension graphs or the
'ultimate tensile stress' (UTS) when referred to stress strain graphs. The ultimate tensile stress is
calculated by dividing the load at D by the original cross-sectional area of the specimen. Although a
useful figure for comparing the relative strengths of materials, it has little practical value since
engineering equipment is not usually operated so near to the breaking point.
From D to E the specimen appears to be stretching under reduced load conditions. In fact the specimen
is thinning out (necking) so that the 'load per unit area' or stress is actually increasing. The specimen
finally work hardens to such an extent that it breaks at L
In practice, values of load and extension arc of limited use since they apply only to one particular size of
specimen and it is more usual to plot the stress-strain curve. (An example of a stress strain curve for a
low-carbon steel is shown in the previous figure.

Fig. Uniaxial tensile loading and Shear loading condition

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Fig.4 Biaxial stress and strain and Principal of strain gauge.

Fig:The basic configuration of a strain gauge.


7.1.2 Compression test: brittle materials are often weaker in tension but strong in compression because
of the presence of submicroscopic cracks, as tensile stress tends to propagate those cracks which are
oriented perpendicular to the axis of tension. The tensile strengths they exhibit are low and usually vary
from sample to sample. These same materials can nevertheless be quite strong in compression. Brittle
materials are chiefly used in compression, where their strengths are much higher. Thats why CT is
important for civil engineering concrete materials and cast iron. Ductile materials are seldom tested in
compression. The specimen is fixed between two flat crossheads one of which remains stationary while
the other is powered either hydraulically or mechanically to give compressive force.

Fig.7.3: The compression test of ductile material

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Fig.: comparison of the compressive and tensile strengths of gray cast iron and concrete, both of
which are brittle materials
7.1.3 Bend tests: to assess whether a material meets fabrication requirements or whether it has desired
design strength. Hence they are classified as:
(a) Ductility (cracking) test to assess the ductility or to verify that the minimum plasticity required of a
material is exceeded. It can be found by using tensile test for determining the percentage elongation.
Another way is a simple bend test. Different ways are applied like close bend, angle bend, 1800 bend and
reverse bend tests. For the last 3, formers of specified nose radius are used.

Fig.7.4 : (a) Close bend test (b) Angle bend test (c)1800 bend test
(b) Transverse tests. It is applied to brittle materials such as cast iron which are highly sensitive to notch
so break in a section away from the gauge length when tensioned. The use of a 3 or 4-point bend test
enables to evaluate critical values of tensile stress required to cause rupture.

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Bending moment diagrams


Fig.7.5: (a) Three point bend test and (b) Four-point bend test
7.1.4 Torsion test: it is aimed at assessing the mechanical behavior of a material under shearing stress.
The testing equipment comprises a twisting head with a chuck for gripping one end of the specimen and
also, measures the twisting moment or torque, and a troptometer for measuring the angle of
deformation. The shear stress increase from zero in the axis to a maximum at the periphery.

Fig.7.6: Torsion in a solid cylindrical specimen


7.1.5 Impact testing: The capacity of a material to withstand shock loads without fracture is called
toughness, impact tests are used to give an indication of the relative toughness of a material. It consists
of striking a suitable specimen with a controlled blow and measuring the energy absorbed in bending or
breaking the specimen. The energy value indicates the toughness of that material.

Fig.7.7 : (a) A rod of high-carbon (1%) steel in the annealed (soft) condition will bend when stuck with
a hammer (UTS 925MPa). (b) After hardening and lightly tempering, the same piece of steel will
fracture when hit with a hammer despite its UTS having increased to 1285MPa
Two types:
- The Izod test: 10mm square notched specimen is used. The striker of pendulum hits the
specimen with KE of 162.72J at a vel. Of 3.8m/s.
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The Charpy test: in Izod test the specimen is supported as a cantilever, but in the
Charpy test it is supported as a beam. It is stuck with a KE of 298.3J at a velocity of 5m/s

Fig.7.8: Standard methods for impact test.


7.1.6 Hardness testing (resistance to deformation or indentation): there are 3 basic principles
employed:
7.1.6.1. Scratch hardness: used by mineralogists and is measured according to mohs
scale (talc=1,
martensite =7, diamond=10)
7.1.6.2. Rebound or dynamic hardness: an elastic ball or hammer is dropped onto the surface to be
tested and hardness is expressed as the energy (resilience) of the impact. The shore scleroscope
measures hardness in terms of height of rebound of the dropping diamond-tipped hammer. The height
of the first rebound indicates the hardness on a 140-division scale.

Fig.7.9: Shore scleroscope used in dynamic hardness testing


7.1.6.3. Indentation: It is of importance to engineers. Three common techniques:
a) Brinell hardness: consists of a steel ball indentor, applied onto the surface to be tested by a load
whose type depends on type and thickness of the metal. It is the load divided by the surface area of the
indentation.

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Fig.7.10: Principle of the Brinnel test

BHN

D
2

d2

P
Dt

[Kg/mm2] Where, P = applied load, D= diameter of

indentor, d = projected diameter of indentation, t = depth of impression. d = Dsin then,

BHN

D 2 1 cos

UTS = 3.45 X BHN for some steels


To choose carefully the combination ball size and load so that indentation is free from distortion and
suitable for measurement:

P
K , for ferrous metals K=30.
D2

b)Vickers hardness: uses diamond pyramid indenter (it is very hard approximately 6000BHN) with an
angle of 1360 between opposite faces. VHN = load/projected surface area of indentation.


2 P sin
2 1.854 P
VHN
2
d
d2
Where P=applied load (kg), d= average length of diagonals (mm), : angle between opposite faces of the
diamond pyramid (1360). There are 3 types of Vickers indentations: Perfect, barreled and pin-cushioned
indentations.

Fig.7.11: Types of Vickers indentations: (a) perfect (b) barreled and (c) pin-cushioned
189

Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy

c) Rockwell tests: the most widely used since it is quick, simple and direct reading. The indenter is either
a conical shaped diamond cone (brale) with an apex angle of 1200 (for hard materials) or a hardened
steel ball (for softer materials). Its principle is to compare the difference in depth of penetration of the
indenter when using forces of two different values. The minor load (preload) is 10Kg and major loads are
60,100 or 150kg.

Fig.7.12: The Rockwell method

HR

k h1 h0
c

Where k = 0.2 for brale and 0.26 for the steel ball, h1, h2: depth of penetration if indenter after the
removal of the major load, and under application of the pre-load, c: the value for scale divisions
(0.002mm).
7.2 NON DESTRUCTIVE TESTING (NDT)
NDT called so bse they are used to establish the fitness of a component or structure for a particular
engineering service without affecting its performance. They detect flaws (break in continuity of a
material, which may be not significant); and/or defects (a flaw which creates a substantial risk or
failure).
They are six:
7.2.1 Visual examination: The most widely used (about 90% of NDT). It is possible to locate and identify
those defects that are visible to the eye. Adequate lighting and accessibility and sometimes, magnifying
lenses are pre-requisites. The accuracy depends on the skills of the operator. It can identify such defects
as surface cracks, scabs, surface porosity, warping and twisting, inadequate filling of the mould.
7.2.2 Dye Penetrant tests (used in plastics and glass): Discontinuities such as cracks that penetrate to
the surface of the material are detected by dye penetrant tests.
The old technique was that of immersing the casting in a bath of hot paraffin of low viscosity and high
surface tension. After being drawn into finest defects by capillary attraction, the cast is removed,
cleaned after which it is painted with whitewash. Paraffin seeping out from the cracks, will discolor the
whitewash and reveal surface defects.
190

Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy

A more modern and more sophisticated technique is illustrated in the Fig.

Fig.7.13: The die penetrant test: (a) a penetrant fills the gap or crack, (b) excess penetrant is removed
from surface and (c) the penetrant is attracted out by a powder developer.
Two types of penetrants can be used: (i) Fluorescent dies, viewed in black (UV) light, and (ii) water
washable colored dies for ordinary light visibility. The developing solution (white powder) spayed onto
the surface reacts with the dye drawing it from the cracks, and it is observed bse it changes the colour
or bse it fluoresces under ultraviolet lamps.
7.2.3 Magnetic particle inspection (MPI)
Magnetic particle testing detects defects surface and near surface (not more than 10mm below the
surface) discontinuities of ferromagnetic materials. A magnetic field is induced in the metal to be tested,
producing line of flux. A metal is placed in a coil; pass the current through the metal or touching the
metal with a yoke or probe. A discontinuity will cause flux leakage in the magnetic field, creating local
north and south poles that attracts magnetic powder particles

Fig.7.14: Magnetic particle inspection techniques: (a) Electromagnetic yoke, (b) Current flow, (c)
Current prods and (d) Magnetizing coil

191

Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy

Fig.7.15 : (a) Orientation of the magnetic field (b) Detecting faults perpendicular to the component
surface.
7.2.4 Eddy currents
When a conducting material is placed into an alternating field, eddy currents are induced in it. These
eddy currents in turn, produce a secondary alternating field. The effect of this secondary field is to
influence or to modify the primary field. This modification can be detected in changes in current and the
impedance, and forms the basis of the eddy current test.
If an alternating magnetic field is linked with any metal object, eddy current will be induced in the
metallic object by electromagnetic induction. A high frequency alternating current is made to flow
through a small coil; as a result, a high frequency alternating field is set up around the coil. This field
induces small electric currents (EC), which circulate in the component and produce magnetic fields in
their own right. These secondary fields react with the field of the induction coil and affect the flow of
current through that coil. The resultant current remains constant as well as there is no change in section
or composition as the induction coil is moving across the component. However, if the induction coil
moves over a crack or other fault in the component, the eddy-current system will be temporally disrupt
and resulting current in the coil will change.

Fig.7.16: The current coil method for eddy current inspection


7.2.5 Ultrasonic testing
Pulse of high frequency oscillations are generated electronically, amplified, and fed into suitable
transducers for conversion into sound waves. Such transducers exploit either magnetostriction (soft iron
192

Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy

changes dimensionally in the presence of alternating magnetic field) or a piezoelectric effect (certain
crystals such as quartz change dimensionally when small electric currents pass through them), the latter
can act as both transmitter and receiver due to their reversibility.
The pulses of high frequency oscillations are driven into the component by the transducer; when the
sound waves meet any discontinuity, the waves are reflected back into the transducer where they are
converted into electrical pulses which can be displayed. The position of discontinuity from the front and
back faces can be determined.

Fig.7.17 : Principles of iltrasonic testing : (a) Ultrasonic testing (b) Typical VDU displays.
Techniques used:
(i) The shadow method: Transmitting and receiving probes are on opposite sides of the specimen. The
reduction in amplitude shows a defect. No debt or location of defect.
(ii) The reflection or pulse echo method: the transducer probe (transmitter and receiver combined) is
placed on one side. Defect echo is received before that of the boundary signal.

Fig.7.18: The shadow and pulse echo flaw detection method


193

Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy

(iii) Transmission with reflection method: its suitable for locating vertical defects in welds. Two
transducers are mounted in one or two probes and used in tandem (employs 2 shear waves) or
delta (employs a shear and compression probe in combination).

Fig.7.19: Tandem and delta technique used in transmission with reflection methods
7.2.6 Radiography
A radiograph is a record of differences in intensity of a radiation produced on a firm. This film is used as
a NDT object for discovering the presence of flaws or defects in a solid material. The X-rays (generated
by accelerating electrons to very high velocities in vacuo and bombarding a suitable material) and
gamma rays (originated from splitting atomic nuclei) are the electromagnetic waves used in industrial
radiography. They can penetrate solid objects bse of their short wavelength (higher frequency than
radio and light waves).
Absorption: the magnitude of radiation absorbed is dependent on the atomic number of element, the
thickness of the specimen and the energy of radiation (wavelength). The basic law of absorption is as
expressed

I I 0 e x Where Io: incident intensity of radiation; I: the transmitted intensity; x: the specimen
thickness and : linear absorption coefficient = m.r (m is the mass absorption coefficient and r is the
physical density of the material)
Consider the radiation intensity across an object shown in fig.: The radiation is more intense in regions
with shortest travel, in accordance to the inverse square law of absorption described by the equation

K
where K is a constant depending on the density of the material.
x2

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Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy

Fig.7.20 : Principles of radiography : (a) General arrangement ;


development.

(b) Appearance of film after

Fig.7.21 : Use of radiography : (a) General arrangement ; (b) Apearance of film after development.

Fig.7.22: Radiation absorption by thickness

195

Integrated Polytechnic Regional Center KIGALI Campus; Mechanical Engineering


Dpt.; Academic year: 2015-2016; Subject: Engineering materials and metallurgy