MEG 311: ENGINEERING METALLURGY

• Metallurgy is the science and technology of separating metals from their ores
and of compounding alloys.

• An alloy is a solid solution either of two or more metals, or of a metal or metals

with one or more nonmetals.

1. Structure of crystalline materials.

2. Phases in Metals; Concept of phase equilibrium; Microstructure of materials.
3. Solidification.
4. Alloying including high strength and heat resistant alloys; non-ferrous metal and
their alloys. Tool steels.
5. The modification of properties through changes in micro structure.
6. Materials strengthening mechanism
7. Metallurgy of casting, brazing, soldering and welding.
8. Modern welding techniques and applications.
9. Weldability of industrial materials.
10. Mechanical working.
11. Non-destructive material testing.

Learning outcomes:
Upon completion of this course, students will:

 Be able to identify phases, eutectics, eutectoid, and peritectic reactions in Fe-C

diagrams, as well as identify simple microstructures that can occur (including
possible effects on mechanical response).

 Given a binary phase diagram, what microstructures can be obtained by suitable

thermal treatments

 Understand and identify different types of strengthening/hardening mechanisms,

alloying, etc.

 Understand and identify all the common mechanical and metallurgical joining
processes, metallurgy of casting, metallurgical joining processes and weldability of
industrial materials

 Understand and identify all the common non-destructive testing techniques

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 Structure of Crystalline Materials

Introduction
Solid materials may be classified according to the regularity with which atoms or
ions are arranged with respect to one another.
A crystalline material: is one in which the atoms are situated in a repeating or
periodic array over large atomic distances; that is, long-range order exists, such
that upon solidification, the atoms will position themselves in a repetitive three-
dimensional pattern, in which each atom is bonded to its nearest-neighbor atoms.
All metals, many ceramic materials, and certain polymers form crystalline
structures under normal solidification conditions.
For those that do not crystallize, this long-range atomic order is absent; these
non-crystalline or amorphous materials. For example (glass) and some of
complex metallic materials. Some of the properties of crystalline solids depend on
the crystal structure of the material.

Lattice Space and Unit Cell:

When describing crystalline structures, atoms (or ions) are thought of as being
solid spheres having well-defined diameters. This is termed the atomic hard
sphere model in which spheres representing nearest-neighbor atoms touch one
another.
An example of the hard sphere model for the atomic arrangement found in some
of the common elemental metals is displayed in Figure (2.1). In this particular
case all the atoms are identical. Sometimes the term lattice is used in the context
of crystal structures; in this sense “lattice” means a three-dimensional array of
points coinciding with atom positions (or sphere centers).

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 Figure (2.1): Lattice space and unit cell

The unit cell:

The atomic order in crystalline solids indicates that small groups of atoms form a
repetitive pattern. Thus, in describing crystal structures, it is often convenient to
subdivide the structure into small repeat entities called unit cells. Is the basic
structural unit or building block of the crystal structure and defines the crystal
structure by virtue of its geometry and the atom positions within.
There are 14 types of crystal structure in various engineering materials as shown in figure
(2.2). The important crystal structures among all of them are:

- The body- centered cubic structure (BCC).

- The face- centered cubic structure (FCC).
- Hexagonal close- packed structure (HCP).

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 Figure (2.2): Types of Crystal structure of materials

The Face-Centered Cubic Crystal Structure

The crystal structure found for many metals has a unit cell of cubic geometry, with
atoms located at each of the corners and the centers of all the cube faces. It is
called the face-centered cubic (FCC) crystal structure. Some of the familiar
metals having this crystal structure are copper, aluminum, silver, and gold.
The mechanical properties of FCC are:
- Low young modulus
- Low yield strength
- Low hardness
- Good ductility and high ability for forming.
Figure 2.3a shows a hard sphere model for the FCC unit cell, whereas in Figure
2.3b the atom centers are represented by small circles to provide a better
perspective of atom positions. The aggregate of atoms in Figure 2.3c represents a

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section of crystal consisting of many FCC unit cells. These spheres or ion cores
touch one another across a face diagonal; the cube edge length a and the atomic
radius R are related through

For the FCC crystal structure, each corner atom is shared among eight unit cells, whereas a
face-centered atom belongs to only two. Therefore, one-eighth of each of the eight corner
atoms and one-half of each of the six face atoms, or a total of four whole atoms, may be
assigned to a given unit cell.

Figure (2.3): a. Hard sphere model of FCC, b. reduced sphere unit cell, and c. crystal
consist many FCC unit cells.

Two other important characteristics of a crystal structure are the coordination

number and the atomic packing factor (APF). For metals, each atom has the
same number of nearest-neighbor or touching atoms, which is the coordination
number.
For face-centered cubic, the coordination number is 12. This may be confirmed
by examination of Figure below; the front face atom has four corner nearest-
neighbor atoms surrounding it, four face atoms that are in contact from behind,
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and four other equivalent face atoms residing in the next unit cell to the front,
which is not shown.

The APF is the sum of the sphere volumes of all atoms within a unit cell (assuming the atomic
hard sphere model) divided by the unit cell volume—that is

For the FCC structure, the atomic packing factor is 0.74, which is the maximum packing
possible for spheres all having the same diameter.

The Body-Centered Cubic Crystal Structure

Another common metallic crystal structure also has a cubic unit cell with atoms
located at all eight corners and a single atom at the cube center. This is called a
body-centered cubic (BCC) crystal structure. A collection of spheres depicting
this crystal structure is shown in Figure 2.4c, whereas Figures 2.4a and 2.4b are
diagrams of BCC unit cells with the atoms represented by hard sphere and
reduced-sphere models, respectively.
Chromium, iron, and tungsten are listed through BCC structure, and their
mechanical properties are:
- High yield strength
- High young modulus
- High hardness
- High tensile strength
- Limited ability to forming.

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 Figure (2.4): a. Hard sphere model of BCC, b. reduced sphere unit cell, and c. crystal
consist many BCC unit cells.

Center and corner atoms touch one another along cube diagonals, and unit cell
length a and atomic radius R are related through

Two atoms are associated with each BCC unit cell: the equivalent of one atom
from the eight corners, each of which is shared among eight unit cells, and the
single center atom, which is wholly contained within its cell.
The coordination number for the BCC crystal structure is 8; each center atom
has as nearest neighbors its eight corner atoms as shown in figure below.

Since the coordination number is less for BCC than FCC, so also is the atomic
packing factor for BCC lower—0.68 versus 0.74.

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The Hexagonal Close-Packed Crystal Structure
Not all metals have unit cells with cubic symmetry; the final common metallic
crystal structure to be discussed has a unit cell that is hexagonal. Figure 2.5a
shows a reduced-sphere unit cell for this structure, which is termed hexagonal
close packed (HCP); an assemblage of several HCP unit cells is presented in
Figure 2.5b.

Figure (2.5): a. a reduced-sphere unit cell and (b) an aggregate of many atoms.

The top and bottom faces of the unit cell consist of six atoms that form regular
hexagons and surround a single atom in the center. Another plane that provides
three additional atoms to the unit cell is situated between the top and bottom
planes. The atoms in this midplane have as nearest neighbors atoms in both of the
adjacent two planes.
The equivalent of six atoms is contained in each unit cell; one-sixth of each of the
12 top and bottom face corner atoms, one-half of each of the 2 center face atoms,
and all 3 midplane interior atoms.
The coordination number and the atomic packing factor for the HCP crystal
structure are the same as for FCC: 12 and 0.74, respectively. See figure below.

Unit cell length a and atomic radius R are related through

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 a = 2R
The HCP metals include cadmium, magnesium, titanium, and zinc; their properties
are:
- Is brittle
- Low yield strength
- Inability to forming

These are some metals listed in Table 2.1.

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Example Problem1:

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 Example Problem 2

DENSITY COMPUTATIONS
Knowledge of the crystal structure of a metallic solid permits computation of its theoretical
density through the relationship

Where:
NA: Avogadro’s number (6.023 × 1023 atoms/mol(
VC : volume of the unit cell
A : atomic weight
n : number of atoms associated with each unit cell

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Example Problem 3:

Problems:
1. If the atomic radius for Pb= 0.175nm, find the volume of the unit cell where Pb is
FCC.

2. Determine the atomic (metallic) radius of Mo where it has BCC crystal structure,
atomic weight = 95.94 g/mole and 𝜌 = 10.2 g/cm3.

Crystallographic Directions:
A crystallographic direction is defined as a line between two points, or a vector.

The following steps are utilized in the determination of the three directional
indices:
1. A vector of convenient length is positioned such that it passes through the
origin of the coordinate system. Any vector may be translated throughout the
crystal lattice without alteration, if parallelism is maintained.
2. The length of the vector projection on each of the three axes is determined;
these are measured in terms of the unit cell dimensions a, b, and c.
3. These three numbers are multiplied or divided by a common factor to reduce
them to the smallest integer values.
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4. The three indices, not separated by commas, are enclosed in square brackets,
thus: [uvw]. The u, v, and w integers correspond to the reduced projections along
the x, y, and z axes, respectively.
For each of the three axes, there will exist both positive and negative coordinates.
Thus negative indices are also possible, which are represented by a bar over the
appropriate index. For example, the [111] direction would have a component in
the (- y) direction. Also, changing the signs of all indices produces an antiparallel
direction; that is, [111] is directly opposite to [111]. The [100], [110], and [111]
directions are common ones; they are drawn in the unit cell shown in Figure 2.6

Figure (2.6): The [100], [110], and [111] directions within a unit cell

Examples:

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Crystallographic Planes
The orientations of planes for a crystal structure are represented in a similar
manner.
Miller indices are specified by three Miller indices as (hkl). Any two planes
parallel to each other are equivalent and have identical indices. The procedure
employed in determination of the h, k, and l index numbers is as follows:
1. The crystallographic plane either intersects or parallels each of the three axes;
the length of the planar intercept for each axis is determined in terms of the lattice
parameters a, b, and c.
2. The reciprocals of these numbers are taken. A plane that parallels an axis may
be considered to have an infinite intercept, and, therefore, a zero index.

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3. If necessary, these three numbers are changed to the set of smallest integers by
multiplication or division by a common factor.
4. Finally, the integer indices, not separated by commas, are enclosed within
parentheses, thus: (hkl).
An intercept on the negative side of the origin is indicated by a bar or minus sign
positioned over the appropriate index.
Examples:

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Liner and Planer Density
Linear density (LD): is defined as the number of atoms per unit length whose
centers lie on the direction vector for a specific crystallographic direction; that is,

Of course, the units of linear density are reciprocal length (e.g., nm-1, m-1).

Planar density (PD): is taken as the number of atoms per unit area that are centered on a
particular crystallographic plane

The units for planar density are reciprocal area (e.g., nm-2, m-2).

Example: Determine the linear and planar density of the [110] direction for the FCC crystal
structure.
Solution:

There are 2 atoms through the vector [110] can be seen from figure (b) and the length of
this vector is 4R so linear density is:

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From figure above:
Consider the section of a (110) plane within an FCC unit cell as represented in Figures a
and b. Although six atoms have centers that lie on this plane (Figure b), only one-quarter of
each of atoms A, C,D, and F, and one half of atoms B and E, for a total equivalence of just 2
atoms are on that plane. Furthermore, the area of this rectangular section is equal to the
product of its length and width. From Figure b, the length (horizontal dimension) is equal
to 4R, whereas the width (vertical dimension) is equal to 2R√2.

Thus, the area of this planar region is and

Examples.1:

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Phases in Metals and Alloys
Phase is a state of matter that is uniform throughout in chemical composition and physical
state. It is a physically distinct and mechanically separable mass of matter. The following
phases may be present in metals in solid state:
1. Solid Solution
2. Intermetallic compound.

Solid solution
A solid solution is formed when two metals which are mutually soluble in the liquid
state remain dissolved in each other after crystallization. If the resulting structure is
examined, even with the aid of a high power electron microscope, no trace can be seen
of the parent metals as separate entities, and if the metals are completely soluble in each
other there will be crystals of one type only.
The term solvent refers to the more abundant atomic form, and solute to the less abundant.
It will be clear that in order that one metal may dissolve in another to form a solid
solution, its atoms must fit in some way into the crystal lattice of the other metal.
This may be achieved by the formation of either a 'substitutional' or an 'interstitial' solid
solution (Fig.1).

Fig.1: Ways in which solid solution can occur

-Interstitial solid solutions

Interstitial solid solutions can be formed only when the atoms of the added element are
very small compared with those of the parent metal, thus enabling them to fit into the
interstices or spaces in the crystal lattice of the parent metal. Not only can this occur
during solidification but, also in many cases, when the parent metal is already solid.
Thus, carbon can form an interstitial solid solution with FCC iron during the solidification

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of steel, but it can also be absorbed by solid iron provided the latter is heated to a
temperature at which the structure is face-centred cubic. This is the basis of carburizing
steel. Nitrogen is also able to dissolve interstitially in solid steel, making the nitriding
process possible; whilst hydrogen, the atoms of which are very small indeed, is able to
dissolve in this way in a number of solid metals, usually producing mechanical brittleness
as a result.

- Substitutional solid solution

In a substitutional solid solution the atoms of the solvent or parent metal are replaced in
the crystal lattice by atoms of the solute metal. This substitution can be either
'disordered' or 'ordered' (Fig.1). Solubility of one metal in another is governed in part by
the relative sizes of their atoms. Thus disordered solid solutions are formed over a wide
range of alloy compositions when the atoms are of similar size but when the atomic
diameters differ by more than 14% of that of the atom of the solvent metal then solubility
will be slight because the atomic size factor is unfavourable.
The size factor effect arises from the strain which is induced in the crystal lattice by a
badly misfitting solute atom. The atoms of the solvent metal are displaced either
outwards or inwards according as the solute atom is either larger or smaller than the
atom of the solvent metal. This distortion of the crystal lattice from the ideal shape
increases the energy of the crystal and tends to restrict solubility in it.
Electrochemical properties of the two metals also influence the extent to which they will
form a solid solution. Thus if the two metals have very similar electrochemical
properties, then they may form solid solutions over a wide range of compositions but
if one metal is very strongly electropositive and the other only weakly electropositive,
then they are very likely to form some type of compound.
As might be expected, the lattice structures of the two metals will influence the extent
to which they are likely to form substitutional solid solutions. If the structures are similar
then it is reasonable to expect that one metal can replace the other satisfactorily in its
lattice. Thus two FCC metals like copper and nickel will form a continuous series of
solid solutions— assisted by the fact that atom sizes of these two metals are almost the
same.
To summarize, a high degree of substitutional solid solubility between two metals is likely
to be obtained when:
1. The difference in atomic radii is less than 14%.
2. Electrochemical properties are similar.
3. The two metals have similar crystal structures.
Even though the size factor of the two metallic atoms may favour their forming a solid
solution they are more likely to form compounds if one is much more strongly
electropositive than the other.

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- INTERMEDIATE COMPUNDS
In many alloy systems, crystal structures or phases are found that are different from those
of the elementary components (pure metals). If these structures occur over a range of
compositions, they are solid solutions. However, when the new crystal structures occur
with simple whole-number fixed ratios of the component atoms, they are intermetallic
compounds with stoichiometric compositions. The difference between intermediate solid
solutions and compounds can be more easily understood by actual examples. When
copper and zinc are alloyed to form brass, a number of new structures are formed in
different composition ranges. The crystal structure of this new phase is body-centered
cubic, whereas that of copper is face- centered cubic, and zinc is close-packed hexagonal.
Because this body-centered cubic structure can exist over a range of compositions (it is the
only stable phase at room temperature between 47 and 50 weight percent of zinc), it is not
a compound, but a solid solution. This is also sometimes called a nonstoichiometric
compound or a nonstoichiometric intermetallic compound. On the other hand, when
carbon is added to iron in an amount exceeding a small fraction of one-thousandth of a
percent at ambient temperatures, a definite intermetallic compound is observed. This
compound has a fixed composition (6.67 weight percent of carbon) and a complex crystal
structure (orthorhombic, with 12 iron atoms and 4 carbon atoms per unit cell) which is
quite different from that of either iron (body-centered cubic) or carbon (graphite).

Material Systems
A material system refers to a definite amount of material or materials.
The components in a system refer to the smallest number or individual substances that
must be listed to describe the chemical composition of the system. These may be elements
(Pb, Sn, Fe, C, etc.) or compounds (H2O, NaCl, etc.)
The phases in a system denote the homogenous parts of the system that are made up of its
components.

Phase diagrams are graphs showing the phases present under selected conditions of
temperature, pressure, and composition when the system is in thermodynamic
equilibrium.
A material system may be specified as in the following example:

Example: Suppose we have 8 gms of copper and 2 gms of nickel. This yields a system
having 80 w/o copper and 20 w/o nickel (w/o= weight percent). This can also be
expressed as mole percent (m/o) or atomic percent (a/o).

8 gm (Cu): (8 gm)/(63.54 gm/mole) = 0.1259 moles

2 gm (Ni): (2 gm)/(58.71 gm/mole) = 0.0341 moles

Since the number of atoms in a mole is constant, the atomic percent is:

8 gm (Cu): 0.1259/(0.1259 + 0.0341) = 78.7 m/o = 78.7 a/o

2 gm (Ni): 0.0341/(0.1259 + 0.0341) = 21.3 m/o = 21.3 a/o

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One-component material systems
The phases possible in a one component system are limited to liquid, solid, and gas states
(Fig 2). A phase diagram consists simply of a graph of pressure vs. temperature, with the
phase regions indicated.

Fig. 2 Phase diagram for a one-component system (water)

Two component material systems

Materials with two components are called binary systems. They are commonly
encountered in engineering materials (brass consisting of copper and zinc, carbon steel
consisting of iron and carbon, etc.) The phase diagram of a binary material is customarily
displayed in a temperature vs. composition format, with the pressure held fixed at
atmospheric.

In the phase diagrams,

L denotes liquid
α, β, γ are various solids
α+ β or L+ γ indicate states where both are present

Two-Components with Complete Solubility: For a system having components completely

soluble in the solid state, the phase diagram is especially simple, since only one phase exists
in the solid state. See Figure 3 for the phase diagram of the material.

Two-Components with Partial Solubility (Eutectic): For a binary system having

components only partially soluble in the solid state, two solid phases will exist, and the
phase diagram is much more complex than Figure 3. A special case is an eutectic diagram
shown in Figure 4. “Eutectic” means that when the two components are mixed, the melting
point is lower than the melting temperatures of the two components separately. At point d,
the eutectic reaction Liquid, L = α + β occur.

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Two-Components with Partial Solubility (Eutectoid): When the liquid region is replaced
by a third solid phase γ, we have the eutectoid reaction γ = α + β and associated phase
diagram. Figure 5 shows such as phase diagram with both a Eutectic and Eutectoid point.

Two-Components with Partial Solubility (Peritectic): For a binary system having

components only partially soluble in the solid state, we may also have a phase diagram
having a peritectic point P, where the reaction L + β = α occurs (Figure 6)

Two-Components with Partial Solubility (Peritectoid): If the liquid in the peritectic

reaction is replaced by a third solid phase, γ, we have a peritectoid reaction α + γ = β. This
is illustrated by Figure 7.

Figure 3: Components with Complete Solubility (Copper-Nickel System). Melting

temperature depends on percentage of nickel. There is a solid phase, then a mixture of
liquid and solid (L + α) and then a complete liquid phase L.

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Figure 4: Two Components with Partial Solubility (Silver Alloy Copper System) At the
Eutectic point (d) the liquid changes to a solid L = α + β (This is at a lower temperature
than when the separate components become solid)

Figure 5: Case 2 - Two Components with Partial Solubility (Iron Carbon System) At Eutectic
point, the liquid changes to a solid L = α + β. At the Eutectoid point γ =α + β. (This is at a
lower temperature than when the change occurs for the individual components)

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Figure 6: Two Components with Partial Solubility – Peritectic. At the Peritectic point, the
reaction L + β = α occurs

Figure 7: Two components with Partial Solubility- Peritectoid Reaction - peritectoid

reaction α + γ = β

Derivation of Lever Rule

Consider a temperature-composition point in a phase diagram where two phases exist, as
shown in Figure 8 for temperature T1 and composition X2. The chemical compositions of
the two phases are:

α - phase: X1 w/o B, 100 - X1 w/o A:

β - phase: X3 w/o B, 100 - X3 w/o A.

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 Figure 8: Phase Diagram for Derivation of Lever Rule

This may be seen by imagining that we start with pure A material and add increasing
amounts of B. When we reach the composition X1 w/o B, the α phase has become saturated
and can accept no additional amount of B. As we add still more B, the second β phase must
appear. The β phase will be saturated, and its composition will be X 3 w/o B, as read from
the right side of the diagram.

Now we would like to determine how much α phase and β phase material will exist at a
temperature T1, and the composition X2 w/o B. To arrive at this, we use the lever rule.

Let A1 be the amount of α phase present,

A3 be the amount of β phase present and
A2 be the total amount of material

The balance of material requires that

A1 + A3 = A2

And the balance of the B material requires that

X1A1 + X3A3 = X2A2

Combining these two equations yields

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which is the fractional weight of the α phase, and

which is the fractional weight of the β phase.

Example: A Cu-Ni alloy (Fig 9) contains 73% cu and 27% Ni at 1200C. Find (1) Weight %
Cu in solid and liquid phases and (2) % of alloy in solid % liquid phases.

Solution: Step 1: Draw horizontal tie line at 1200C Step 2: Project down for Cu

Liquid, 𝑊L = 80%Cu
Solid, 𝑊S = 70%Cu
Step 3: For 𝑊0 = 27% Nickel, project up to tie line

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The fraction of alloy liquid is

𝑊 𝑊
𝑊 𝑊

The fraction of the alloy that is solid is

𝑊 𝑊
𝑊 𝑊

Example: Consider the lead-tin (Pb-Sn) diagram shown in Figure 20. For an alloy
consisting of 40 w/o Sn determine the composition and amount of the α and β phases
present at 100oC. Also, determine the relative amount of material formed from the eutectic
reaction.

Figure 20: Lead-Tin Phase Diagram

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Solution: At T1 (100oC), the composition of the α phase is
5 w/o Sn, 95 w/o Pb
The amount of the α phase present is

The composition of the β phase is

99 w/o Sn, 1 w/o Pb
The amount of the β phase present is

To determine the amount of material that experienced the eutectic reaction, we note that
just above the eutectic temperature of 183oC, the remaining liquid had the eutectic
composition 62 w/o Sn and 38 w/o Pb. The amount of remaining liquid was (40 - 19)/ (62
- 19) = 48.8%. On cooling below the eutectic temperature, this liquid experienced the
eutectic reaction L = α + β. The amount of eutectic material present at 100oC is 48.8 % (by
weight). The amount of α and β phase present in the eutectic material at 100oC is (99 -
62)/(99 - 5) = 39.4 % α, 60.6 % β.

Iron-Carbon Systems
Alloys of iron and carbon form the system for common steels and cast irons. Generally,
steels have carbon content between 0 and 2 % by weight, while cast irons have carbon
content between 2 and 5 % by weight. The iron-carbon phase diagram is shown below in
Figure 19.

The phases are defined as follows:

i. Ferrite α phase: BCC crystalline phase
ii. Austenite γ: FCC crystalline phase
iii. δ phase: high temperature BCC crystalline phase
iv. Cementite or carbide Fe3C: mixture; intermediate compounds
v. Pearlite: layered two phase mixture generated by transforming austenite to ferrite
and carbide by the eutectoid reaction γ = α + Fe3C
vi. Martensite: a non-equilibrium phase in steels formed by rapid cooling of austenite.
It arises because, with extremely rapid cooling, there is insufficient time for the
carbon atoms to realign themselves from their locations within the FCC structure of
austenite to their locations in the BCC structure of ferrite. As a result, the structure
is "trapped" between FCC and BCC, and actually results in a body centered
tetragonal lattice. Martensite is very hard and brittle, and by itself, has very few
practical applications. Its value lies in combinations of ferrite and martensite
obtainable by various heat treatments.
vii. Bainite: mixture of ferrite and cementite formed by isothermal transformation of
austenite under selected conditions.

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Figure 19: Iron-Carbon Diagram

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 Fig 20

Eutectoid Point for Iron-Carbon Systems

The eutectic and eutectoid points on the phase diagram are important for heat treatment.
The eutectoid point for Iron-Carbon is at a temperature of 727 C and 0.77% carbon by
weight. See the figure below (fig 21) for an enlarged view of this region of the phase
diagram.
i. Eutectoid steel has exactly 0.77% carbon. When cooling below the eutectoid
temperature (727 C) it becomes 100% Pearlite. The resulting steel is high strength
and wear resistant, used for things like music wire or railway track.

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 ii. Hyper-Eutectoid has more than 0.77% carbon content. When cooling below the
eutectoid temperature, it forms a combination of cementite and pearlite. This is
more brittle.
iii. Hypo-Eutectoid has less than 0.77% carbon content. When cooled below the
eutectoid temperature, it forms a combination of pearlite and ferrite. This is more
ductile.
The lever rule, discussed earlier, can be used to determine the proportions.

Fig 21

Time-Temperature-Transformation (TTT) Diagrams for Iron-Carbon Systems

Suppose we rapidly cool steel of eutectoid composition (0.8 % C) from the austenitic range
down to some temperature where α and Fe3C are the stable phases. If we could observe
the resulting transformation process, we would find that, initially, the material is 100%
unstable austenite. After some time, the ferrite and cementite would begin to form (either
as pearlite or bainite) and after sufficient time, the transformation of the austenite would
be complete. This process is represented by the so-called Time-Temperature-
Transformation (TTT) diagram shown in Figure 22.

Notice that, if we suddenly cool the austenite to a temperature Ms (martensite start) or less,
some martensite will form. The remaining austenite will then transform to bainite. If we
suddenly cool the material to temperature Mf (martensite finish), we will have 100%
martensite and no further transformation will occur.
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 Figure 22: TTT Diagram for Steel

Strengthening Mechanisms

What is happening in material during plastic deformation?

· Dislocations and Plastic Deformation

 Motion of dislocations in response to stress
 Slip Systems
 Plastic deformation in
 Single crystals
 Polycrystalline materials
· Strengthening mechanisms
 Grain Size Reduction
 Solid Solution Strengthening
 Strain Hardening

Introduction
Why metals could be plastically deformed?
Why the plastic deformation properties could be changed to a very large degree by forging
without changing the chemical composition?
Why plastic deformation occurs at stresses that are much smaller than the theoretical
strength of perfect crystals?

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Plastic deformation – the force to break all bonds in the slip plane is much higher than the
force needed to cause the deformation. Why?

These questions can be answered based on the idea proposed in 1934 by Taylor, Orowan
and Polyani: Plastic deformation is due to the motion of a large number of
dislocations. Dislocations allow deformation at much lower stress than in a perfect
crystal.

If the top half of the crystal is slipping one plane at a time then only a small fraction of the
bonds are broken at any given time and this would require a much smaller force.

The propagation of one dislocation across the plane causes the top half of the crystal to
move (to slip) with respect to the bottom half but we do not have to break all the bonds
across the middle plane simultaneously (which would require a very large force).
The slip plane – The crystallographic plane of dislocation motion.

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Direction of the dislocation motion

Edge dislocation line moves parallel to applied stress

Screw dislocation line moves perpendicular to applied stress

For mixed dislocations, direction of motion is in between parallel and perpendicular to the
applied shear stress.

34
Strain field around dislocations

Dislocations have strain fields arising from distortions at their cores -strain drops
radially with distance from the dislocation core

Edge dislocations introduce compressive, tensile, and shear lattice strains, screw
dislocations introduce shear strain only.

35
Interactions between dislocations

The strain fields around dislocations cause them to interact (exert force on each other).
When they are in the same plane, they repel if they have the same sign (direction of the
Burgers vector) and attract/annihilate if they have opposite signs.

36
Where do dislocations come from?
The number of dislocations in a material is expressed as the dislocation density - the total
dislocation length per unit volume or the number of dislocations intersecting a unit area.
Dislocation densities can vary from 105 cm-2 in carefully grown metal crystals to 1012 cm-
2 in heavily deformed metals.
Most crystalline materials, especially metals, have dislocations in their as-formed state,
mainly as a result of stresses (mechanical, thermal...) associated with the forming
process.

Figure: Computer simulation of Frank-Read source: Emission of dislocation loops from a

dislocation segment pinned at its ends

The number of dislocations increases dramatically during plastic deformation. Dislocations

spawn from existing dislocations, grain boundaries and surfaces.

37
Figure: Simulation of plastic deformation in a FCC single crystal (Cu) of linear dimension 15
micrometers

Slip Systems
In single crystals there are preferred planes where dislocations move (slip planes). Within
the slip planes there are preferred crystallographic directions for dislocation movement
(slip directions). The set of slip planes and directions constitute slip systems.
The slip planes and directions are those of highest packing density. Since the distance
between atoms is shorter than the average, the distance perpendicular to the plane has to
be longer than average. Being relatively far apart, the planes can slip more easily relatively
to each other. BCC and FCC crystals have more slip systems as compared to HCP,
there are more ways for dislocation to propagate ⇒ FCC and BCC crystals are more ductile
than HCP crystals.

Slip in single crystals - resolving the applied stress onto the slip system
Dislocations move in particular directions on particular planes (the slip system) in
response to shear stresses applied along these planes and directions ⇒ we need to
determine how the applied stress is resolved onto the slip systems. When the resolved
shear stress becomes sufficiently large, the crystal will start to yield (dislocations start to
move along the most favorably oriented slip system).

Slip in a single crystal

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 Plastic Deformation of polycrystalline materials
 Grain orientations with respect to applied stress are random.
 The dislocation motion occurs along the slip systems with favorable orientation
(i.e. that with highest resolved shear stress).

 Larger plastic deformation corresponds to elongation of grains along direction of

applied stress.

Before After

39
  Slip directions vary from crystal to crystal ⇒ Some grains are unfavorably
oriented with respect to the applied stress
 Even those grains for which shear stress is high may be limited in deformation by
adjacent grains which cannot deform so easily
 Dislocations cannot easily cross grain boundaries because of changes in direction
of slip plane and atomic disorder at grain boundaries
 As a result, polycrystalline metals are stronger than single crystals (the
exception is the perfect single crystal without any defects, as in whiskers.

Strengthening
 The ability of a metal to deform depends on the ability of dislocations to
move.
 Restricting dislocation motion makes the material stronger.

Ordinarily, strengthening reduces ductility. Mechanisms of strengthening in single-

phase metals include:

 Grain-size reduction
 Solid-solution alloying
 Strain hardening

1. Strengthening by grain-size reduction

Grain boundary barrier to dislocation motion: slip plane discontinues or change

orientation. Small angle grain boundaries are not very effective in blocking dislocations.

40
High-angle grain boundaries block slip and increase strength of the material. A
stress concentration at end of a slip plane may trigger new dislocations in an adjacent
grain. The finer the grains, the larger the area of grain boundaries that impedes dislocation
motion. Grain-size reduction usually improves toughness as well. Usually, the yield
strength varies with grain size d according to Hall-Petch equation:

where σo and ky are constants for a particular material, d is the average grain diameter.

Figure: Yield strength and grain size for 70Cu-30Zn brass alloy

Grain size d can be controlled by the rate of solidification, by plastic deformation and
by appropriate heat treatment.

2. Solid-Solution Strengthening
Alloys are usually stronger than pure metals. Interstitial or substitutional impurities
cause lattice strain. As a result, these impurities interact with dislocation strain fields and
hinder dislocation motion. Impurities tend to diffuse and segregate around dislocation
cores to find atomic sites that suit their radii. This reduces the overall strain energy and
“anchors” the dislocations. Motion of a dislocation core away from the impurities moves it
to a region of lattice where the atomic strains are greater (i.e. the dislocation strains are no
longer compensated by the impurity atoms).
41
Smaller and larger substitutional impurities tend to diffuse into strained regions around
dislocations, leading to partial cancellation of impurity-dislocation lattice strains.

42
43
 3. Strengthening by increase of dislocation density
(Strain Hardening = Work Hardening = Cold Working)
Ductile metals become stronger when they are deformed plastically at temperatures well
below the melting point. The reason for strain hardening is the increase in dislocation
density with plastic deformation. The average distance between dislocations decreases
and dislocations start blocking the motion of each other.
The percent cold work (%CW) is often used to express the degree of plastic deformation:

where A0 is the original cross-section area, Ad is the area after deformation.

%CW is just another measure of the degree of plastic deformation, in addition to strain.

New yield strength is higher than the initial yield strength. The reason for this effect is
strain hardening.

44
Figure: Yield strength and hardness are increasing as a result of strain hardening but ductility
is decreasing (material becomes more brittle).
PRINCIPLES OF SOLIDIFICATION OF METALS
Solidification is a phase transition in which a liquid turns into a solid when its
temperature is lowered below its freezing point. Solidification occurs by two processes:
nucleation and growth.

Why to study in detail?

The solidification of metals and their alloys is important in various industrial processes. Most
of the components produced from metals are by casting process. When a metal is welded a
small portion of metal near the weld melts and resolidifies. During solidification, the liquid
changes in to solid as cooling proceeds. The energy of liquid is less than that of the solid above
the melting point. Hence liquid is stable above the melting point. But below the melting point,
the energy of liquid becomes more than that of the solid. Hence below the melting point, the
solid becomes more stable than the liquid.

Thermodynamically, both liquid and solid have equal energy at melting point and therefore
both are equally stable at melting point. Freezing is almost always an exothermic process,
meaning that as liquid changes into solid, heat is released. This heat must be continually
removed from the freezing liquid or the freezing process will stop. The energy released upon
freezing is a latent heat and is the entropy part. Some under-cooling will be essential for
solidification.

Casting process and welding process

Cooling Curves
A cooling curve is a graphical plot of the changes in temperature with time for a material over
the entire temperature range through which it cools. Total heat to be removed for
solidification,
( )

( ( )
 Cooling curve of pure metals

Cooling curve with undercooling

Nucleation
The first step of metal solidification is the creation of tiny, stable, nuclei in the liquid metal.
Cooling the liquid below its equilibrium freezing temperature, or undercooling, provides the
driving force for solidification. Once a cluster reaches a critical size, it becomes a stable
nucleus and continues to grow. The mold walls and any solid particles present in the liquid
make nucleation easier.
Cluster of atoms Embryo Nuclei Crystals Grains

r > r’ r < r’ r’ = critical radius

 Nucleation and formation of grains

Nucleation is of two types-

Homogeneous nucleation: Formation of a critically sized solid from the liquid by clustering
together of a large number of atoms at a high undercooling.
Heterogeneous Nucleation: Formation of a critically sized solid from the liquid on an
impurity surface. Heterogeneous nucleation occurs in a liquid on the surface of its container,
insoluble impurities and other structural materials that lower the critical free energy
required to form a stable nucleus. In practice, homogeneous nucleation rarely takes place
and heterogeneous nucleation occurs either on the mould walls or on insoluble impurity
particles.

Types of Nucleation

Once solid nuclei form, growth occurs as atoms are attached to the solid surface. Growth is the
physical process by which a new phase increases in size. In the case of solidification, this refers
to the formation of a stable solid particle as the liquid freezes. Nature of growth of solid
depends on how heat is removed from the system. Sensible heat and latent heat is to be
removed. The manner in which the latent heat is lost determines the growth mechanism.
There are two growth mechanisms namely planar growth and dendritic growth. The difference
in planar and dendritic growth arises because of the differences in sink for the latent heat.
Planar growth: The heat is dissipated through the crystal, i.e. the growing crystal is colder
than the melt. Here a solid bulge into the liquid would melt again because the temperature in
the bulge is above Tm. Therefore, one obtains a stable flat solidification front. Any small
protuberance that begins to grow on the interface is surrounded by liquid above the freezing
temperature. The growth of the protuberance stops until the remainder of the interface
catches up with it. This planar growth occurs by the movement of a smooth solid-liquid
interface into the liquid.
Dendritic growth: For a strongly undercooled melt the heat of crystallization can also be
dissipated through the melt. Under these conditions a small solid protuberance called a
dendrite which forms at the interface is encouraged to grow. As the solid dendrites grow;
there is transfer of latent heat of fusion into the undercooled liquid thereby raising the
temperature of the liquid towards freezing temperature. Dendritic growth continues until the
undercooled liquid warms to the freezing temperature. Any remaining liquid then solidifies by
planar growth. These are thermal dendrites different from dendrites in alloys.

Planar growth and dendritic growth

Solidification Defects
Shrinkage: Most materials contract or shrink during solidification and cooling. Shrinkage can
sometimes cause cracking to occur in component as it solidifies. Shrinkage is the result of:
i. Contraction of the liquid as it cools prior to its solidification
ii. Contraction during phase change from a liquid to solid
iii. Contraction of the solid as it continues to cool to ambient temperature.
To minimize the damaging effects of shrinkage RISER is used in casting process. Riser is a
reservoir of molten metal to compensate the shrinkage. Thus molten metal is continually
available from risers to prevent shrinkage voids. It is desirable for regions of the casting most
distant from the liquid metal supply to freeze first and for solidification to progress from these
remote regions toward the riser. Also to minimize shrinkage problems with final cast product,
an allowance is given for the size of the mould during pattern design.
Gas porosity: Many metals dissolve a large quantity of gas when they are liquid. However
when metal solidify they retain only a small part of the gas. But these form bubbles trapped in
the solid metal producing gas porosity.

Heat Treatment of Steel: The modification of properties through changes in micro

structure
By varying the amount of martensite present in the material, the mechanical properties of the
steel can be varied. Martensite alone is very hard and strong but also is extremely brittle. A
compromise between strength and ductility can be reached by varying the amount of
martensite present in equilibrium with ferrite and carbide.
The procedure for forming this mixed material is called "heat treatment." First, the material is
rapidly cooled (quenched) so as to form nearly 100% martensite. At room temperature, this
non- equilibrium phase is, for all practical purposes, stable and will not further transform to
ferrite and carbide. If we then take the 100% martensite and heat it to an elevated
temperature (say 700o C) and hold it there for some length of time (tempering), the
martensite can be softened (stress relieved) and decompose. The changes that occur are
temperature dependent and range from merely a reduction in strain-energy and dislocation
density to microstructural changes within the martensite itself. The end result is a material
that retains some of the high strength and hardness characteristics of pure martensite while
restoring some ductility.
As shown in Figure 25, the hardness obtainable with martensite is dependent on the carbon
content. Since it is the "trapping" of the carbon atoms which forms martensite, and thus
hardens the metal, pure iron cannot be hardened by quenching

Fig. 24 Heat Treatment of Eutectic Steel

Specifics of Quenching Process for Iron-Carbon Systems
The rate of cooling affects the resulting grain structure and thus the hardness, ductility, and
strength of the steel specimen. Quenching is typically achieved in one of the following
mediums. From fastest to slowest, steel can be quenched in brine (fastest), water (second
fastest), air, or molten salt (slowest). We often use Time-Temperature-Transformation curves
(TTT Curves), described earlier, to predict a steel’s properties after heat treatment. The
following discussion uses figure 26, below.
The first step in any heat treatment process is to heat the material above 727.:C. This step is
called austenitizing.
The dark blue curved lines on the diagram indicate the start and end of the transformation
from austenite to pearlite. Each of the lines labeled (a)—(g) indicate idealized cooling curves
(remember that the rate of cooling affects the transformation rate):
Curve (a) shows a steel sample rapidly quenched in brine or water. The idealized cooling curve
never approaches the transformation to pearlite, and therefore all austenite (ϒ) is converted to
Martensite. Martensite is an extremely hard and strong crystal structure with a very low
ductility. It is rarely used structurally without tempering. The temperature at which austenite
will transform to martensite is around 250:C
Curve (b) shows steel that is heated to 727 :C, hot quenched (in molten salt) to ~695 :C, and
held at that temperature for over 2 hours to form 100% coarse pearlite. 100% coarse pearlite
is very ductile as hot quenching removes strain-induced stresses, but it is also soft and weak.
Curve (c) shows steel that is heated to 727 :C, hot quenched to 610 :C, and held at that
temperature for over 3 minutes to form 100% fine pearlite. 100% fine pearlite has a uniform
structure and higher strength than coarse pearlite. The cutoff between coarse and fine pearlite
varies but is around 650 :C.
Curve (d) shows steel that is heated to 727 :C, hot quenched to 580 :C, held for ~5 seconds
then water quenched to form a structure of 50% fine pearlite and 50% martensite.
Curve (e) shows steel that is heated to 727 :C, quenched to ~475:C, and held for over 3
minutes to form upper bainite. Bainite is an intermediate structure between pearlite and
martensite. It forms between 250 - 550 :C. Upper Bainite is distinguished by its coarser
cementite particles. IT forms between 330 – 550 :C.
Curve (f) shows steel that is heated to 727 :C, quenched to ~295:C, and held for over 2 hours
to form lower bainite. Lower bainite is characterized by its finer cementite particles.
Curve (g) shows a steel that is heated to 727 :C, cooled to ~300 :C, and held for 30 minutes
then rapid quenched (in water) to form 50% lower bainite and 50% martensite.

Fig 26: TTT Diagram of Eutectoid Steel

Case Hardening of Steel
Case Hardening is when metal is placed inside a carbon-rich environment. It is heated to very
high temperatures to introduce carbon to the outside of the structure. This results in a hard
outer surface, but a tough and strong inner surface. The process involves diffusion, following
Fick’s Second Law.
Fick’s second law tells us that when case hardening steel, the carbon concentration in air at the
surface, Cs, the carbon concentration at some distance x into the surface, Cx, and the initial
carbon concentration of the steel, Co, can be related according to:

√
where D is the diffusivity constant in m2/s and t is time.

Metallurgy of Welding
Welding is a complex process that involves:
- Gas-metal & slag-metal reactions
- Solidification
- Metallurgical reactions in the solid state
• Annealing and Recovery
• Grain growth
• Precipitation
• Phase transformation
These metallurgical phenomena control weld strength and ductility

Gas-Metal Reactions
• Reactive gases (especially N2, O2, H2) may be present in the arc atmosphere due to surface
contamination, imperfect shielding, or purposeful additions.
• These gases dissociate in the arc and react rapidly with the high temperature, turbulent
liquid metal in the weld pool.
• Once dissolved in the metal, oxygen and nitrogen combine with deoxidizers such as Si or AI.
The resulting oxides or nitrides remain as small inclusions in the weld metal.
• Excess dissolved gas is rejected during solidification and may cause porosity (e.g. hydrogen
in AI)
• Dissolved hydrogen can cause cracking in steels.

Slag-Metal Reactions
• Fluxes and slags interact with the molten weld metal
• The slags used in flux shielded processes are designed to absorb deoxidation products and
other contaminants -
• The cleanliness and properties of the weld metal depend on the oxidation potential of the arc
atmosphere and on the type of flux
• Highly basic fluxes reduce weld metal oxygen content and give superior notch toughness.
Acid fluxes tend to give higher oxygen contents and poor notch toughness.
• Fluxes may also be used to modify weld metal composition by transfer of alloying elements
from the slag to the liquid metal.
Dilution
• Dilution results from mixing of filler and base metals
- Dilution ratio is the mass of base metal melted divided by the total mass of melted metal
• Weld pool mixing results in a uniform fused zone, except when large differences exist
between filler and parent composition
• A sharp boundary lies between the fused zone and base metal
• Dilution is influenced by joint preparation, welding process and procedure

Solidification
Factors controlling the solidification modes of metals are:
- Temperature gradient
- Composition
- Rate of solidification

Figure: Weld solidification microstructures

Annealing and Recrystallization

• Welding has little effect on the properties of annealed single phase alloys that are
strengthened by solution strengthening e.g. hot rolled low carbon steels, austenitic stainless
steels, commercially pure aluminum, titanium and zirconium.
• However, when such materials are strengthened by cold work, the weld thermal cycle
induces recrystallization and grain growth
• The welding heat anneals the heat affected zone, reducing its strength and increasing
ductility

Figure x: the effect of cold work and annealing

Figure xx: showing the weld and HAZ

 Engineering Metallurgy

Phase Transformations
•The properties of steels are influenced by the phase transformations they undergo on
heating and cooling
• Iron solidifies as a body-centred crystal structure named delta- ferrite
• On further cooling it transforms to a face-centred cubic crystalline phase called gamma
iron or austenite
• The austenite subsequently transforms back to a body-centred cubic form known as
alpha iron or ferrite

A welded joint consists of:

i. Weld metal
Melted and re-solidified base metal mixed with filler metal (if added)
ii. Heat affected zone (HAZ)
iii. The region around the weld whose properties or microstructure are affected by the
thermal cycle- reheating also alters the structure of under1ying weld metal in multi-
pass welds; and
iv. Base metal

Welding defects
1. Incomplete fusion and joint penetration.
2. Inclusions: oxides, slag and tungsten.
3. Geometric imperfections: undercutting, underfill, excessive reinforcement, surface
irregularities, drop through and mismatch.
4. Metallurgical Defects:
a) Defects related to segregation: hot cracking and micro fissures; cold cracking, delayed
cracking, porosity and subsurface shrinkage.
b) Imperfections induced by metallurgical reactions: embrittlement; metallurgical notches.
5. Other imperfections: arc strikes, weld spatter

When a weld is made, following factors occur:

i. The changes of temperature
ii. The growth of dimensions
iii. The phase transformation etc.
The rate of cooling or quench is of primary importance and this is controlled by the
process, procedure, metal and mass.

Example: The electroslag has the lowest cooling rate among welding methods, while the
gas metal arc has a much faster cooling rate.
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Engineering Metallurgy

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 Engineering Metallurgy

The heat-affected-zone (HAZ)

The area between the interface of the deposited weld metal, and extending into the base
metal far enough that any phase change occurs, is known as the heat-affected-zone (HAZ).

HAZ is a portion of the weld since it influences the service life of the weld.

HAZ is the most critical in many welds. For instance, when welding hardenable steel HAZ
can increase in hardness to an undesirable level. When welding hardened steel, HAZ can
become a softened zone since the heat of the weld has annealed the hardened metal.
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 Engineering Metallurgy

Metal Processing: Mechanical working

Manufacturing processes can alter crystal microstructure and thus influence the strength,
ductility, and impact toughness of a material. While a variety of finishing processes are
suited to specific applications, we will focus on casting, hot and cold rolling, extrusion,
forging, and drawing.

Casting:
Molten metals can be cast into large ingots in a direct chill casting unit. These large ingots
are typically rolled into sheets or plates, or else extruded into structural shapes like I-
Beams. Metals can also be cast into smaller, complex shapes using metal or sand molds.

Fig 10 Casting

Hot and Cold Rolling:

To make large sheets or plates, large ingots are often hot-rolled initially (to allow for a
larger thickness change). A schematic is shown below. The hot rolling process continues
until the plate reaches its desired thickness or until it cools such that rolling becomes
impossible. Plates will be reheated and rolled until they reach the desired thickness.

Fig. 11 Hot Rolling

After hot rolling, plates are usually cold rolled. Cold rolling hardens and strengthens the
metal by introducing internal stresses (dislocations) in the material microstructure. To re-
soften the material, remove internal stresses, and improve toughness, the material may be
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reheated in a process called annealing.

The amount of cold working is often expressed as a percentage related to the change in a
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material’s thickness, i.e.:

 Engineering Metallurgy

Where %CW indicates the percent cold work done on a material, tho and thf indicate the
initial and final thickness of the material, respectively.

Extrusion:
Extrusion is the forming of a material through plastic deformation by forcing it though a die
under high pressure. Cylindrical rods and hollow tubes of most metals are fabricated this
way. This process is often used to form a wide variety of cross sections for aluminum,
copper, and their alloys.

Fig 12 Extrusion

Forging:
Forging is the process of a material being pressed or formed into its desired shape, which
can be irregular (unlike rolling or extruding). The temperature of forging is important for
the final strength, hardness, and ductility of the material. Typically forged metals are
tougher and more durable than cast metals. Forging involves hot and cold working by
nature, and can act to reduced voids in the metal’s microstructure.

Fig 13 Forging

Drawing:
Drawing is a cold working process typically used to make wire, in which a metal rod (such
as copper) is pulled through a carbide nib. Deep drawing is a form of drawing in which a
punch and die are used to form cup-shaped objects from sheet metal. Aluminum cans are
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formed by deep drawing.

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 Engineering Metallurgy

Drawing is a form of cold work, and the percentage of cold work can be expressed in a 2-D
analogy to the equation for rolling:

Where Axc,o and Axc,f indicate the initial and final cross-sectional areas of the metal rod,
respectively.

Fig 15 Drawing

Work Hardening and Annealing

When a material is plastically strained the yield stress is increased. In many of the
manufacturing techniques listed earlier, the material is plastically deformed in order to
fabricate the desired shape. As Figure 16 shows, although this may significantly increase
the yield strength of the material, it also makes it more brittle. This change is a result of the
dislocation density, or imperfections in the lattice, increasing as a result of the deformation.

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