Metallurgical Design

of Flat Rolled Steels

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Metallurgical Design
of Flat Rolled Steels

Vladimir B. Ginzburg
International Rolling Mill Consultants
Pittsburgh, Pennsylvania, U.S.A

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 PREFACE

During the last several decades, the concept of metallurgical design has been applied to the
development of flat-rolled steel products to obtain an optimum combination oftheir mechanical and
manufacturing properties. The desired steel properties are achieved by the proper selection of steel
chemical composition in combination with the selection of an optimal processing route that may
include steelmaking, casting, slab reheating, hot rolling, cooling, cold rolling, annealing and other
heat treatment processes. In his previous three books Steel-Rolling Technology: Theory and
Practice, High-Quality Steel Rolling: Theory and Practice, and Flat Rolling Fundamentals, the
author outlined the state-of-the-art in the development of technology for rolling of flat rolled
products with the required geometrical parameters. This book is mainly concerned with metallurg-
ical aspects of rolling of flat steel products and obtaining the steels with the required combination
of mechanical properties. Metallurgical design of steels processed in rolling mills is frequently
assisted by computer modeling, allowing one to reduce the number of trials prior to obtaining a steel
with desired properties. In application to a particular rolling mill, these computer models may assist
in achieving two principal objectives: further improvement in the properties of the products that are
currently produced by the mill, and the development of new products with required properties that
can be produced by the rolling mill.
To accomplish these two objectives, the computer model must have the following attributes:

• Capability to take into consideration the limits imposed by either current or potentially
upgraded capacity of a rolling mill
• Capability to be accurately calibrated to simulate the evolution of microstructure and
properties for the products currently produced by a rolling mill
• Capability in extrapolation, i.e. the capability to be accurate in predicting the evolution of
microstructure and properties for new products and rolling conditions different from those
that existed during the calibration of the model.

To take into account the limits imposed by mill capacity, one can readily adapt the rolling
process models for hot strip and plate mills that have already been developed during the past several
decades. Besides defining mill limits for rolling a newly developed product, rolling process models
can also calculate the input parameters needed by a metallurgical model, such as rolled material
temperature, strain, strain rate, and process time. Calibration of the rolling process models is usually
 PREFACE

accomplished with high accuracy. This is due to the fact that the parameters used by these models
are measured in real time not only during a final rolling stage but also during most of the
intermediate stages of the rolling process, providing a viable information for improving their
accuracy. Unfortunately, this is not the case with metallurgical models. In these models, the most
critical parameters, such as phase composition, grain size, and mechanical properties, cannot be
measured during intermediate or final stages of a rolling process, and are usually measured much
later by using laboratory test equipment.
This fact makes calibration of the metallurgical models much more difficult. This problem can
be alleviated by reducing the number of variables that are used by the metallurgical model to
describe the intermediate stages of rolling process. This, however, must be done with great care in
order to avoid the omission of some essential physical processes that must be included to assure
extrapolating properties of the model.
In the most general case, the Metallurgical Design Model includes five main components:

1. Heat Transfer Model

2. Steel Deformation Model
3. Rolling Process Model
4. Microstructural Evolution Model
5. Steel Properties Model.

The first three models have been developed during the last three decades. They were used
successfully in off-line computer models for designing new rolling mills, upgrading and optimizing
operating practices of existing rolling mills, and also for mill online control systems. All this was
accomplished in application to a great variety of steels and exotic alloys, including superalloys that
are several times harder to roll than low carbon steel. Microstructural evolution model and steel
properties model are the latest additions that will extend the application of computer modeling to
designing steels with desired mechanical properties.
It is commonly accepted that the metallurgical model must describe the following principal
physical processes that occur during hot rolling of steels:

• Grain restoration process

• Solubility of microalloy carbides and nitrides
• Precipitation of microalloy carbides and nitrides
• Inhibition of recrystallization by precipitation
• Strengthening mechanisms in steels
• Microstructural evolution during rolling and cooling
• Decomposition of austenite to ferrite and other phases.

Ultimately, the model must establish the relationship between the properties ofthe produced steel
and the microstructure obtained at the end of the rolling process, and, in some cases, after a
subsequent heat treatment. This task is overwhelming. Fortunately, in the process of developing
a metallurgical model, one can make use of a wealth of information available nowadays regarding
both theoretical and experimental research in metallurgical aspects of hot rolling process. In doing
 PREFACE

so, however, one must overcome some difficulties in applying this information because of a variety
oftheoretical assumptions and experimental conditions that were used by different research workers,
explaining appreciable differences between their results obtained for the same types of steels.
Adding to this confusion are the various forms of equations developed by different research workers
to describe the same physical phenomenon.
This book outlines the basic principles of metallurgical design that are currently used in
application to flat-rolled steel products. The author reduced some known equations describing the
same physical phenomena to common general forms. The obtained algorithms take into account the
variables used by many research workers, thus simplifying the process of objective comparison of
their equations. The results of this comparison are mostly applied to the plain C-Mn and some
microalloyed steels. They indicate a substantial disagreement between different research workers
regarding to the quantitative effects of various material and process parameters on both the
microstructural evolution and the properties of produced steels. However, there is a certain
consensus regarding the qualitative effects of these parameters. This opens the way for further
perfection ofknown algorithms applicable to the plain C-Mn and some microalloyed steels, and also
for the development of algorthims applicable to other types of steels, including extra and ultra low
carbon steels, ferritic steels, bainitic steels, multiphase steels, and the steels for various special
applications.
During the last several decades, significant progress has been made in the accumulation of
knowledge related to the microstructural evolution in flat-rolled steel products. The process was
described not only in physically-based qualitative terms, but also, for some steels, in quantitative
terms. A wealth of experimental data was produced based on both laboratory and mill production
tests. The state-of-the-art in this area, however, has not reached the point when it becomes possible
to develop a universal model that is applied to any required combination ofproperties of steels, wide
range of possible steel chemical compositions, and subjected to every known thermomechanical
process. To this date, practically viable models for metallurgical design have been developed only
in application to the limited groups of steels produced by narrowly defined thermomechanical
processes. A further expansion of application of these models to a wider range of steel grades
requires further accumulation ofknowledge that is concerned with the microstructural evolution in
flat-rolled steel products. The author hopes that this book will be helpful in this challenging
endeavor.
The author thanks his former and current colleagues who worked with him during the last three
decades on the development of computer models for simulation of rolling conditions in both hot and
cold mills. My special gratitude goes to my wife Tatyana for her great contribution in preparing this
book and her constant encouragement and support.

VLADIMIR B. GINZBURG
 CONTENTS

Preface lll

Part I Main Characteristics of Steel

Chapter 1 Microstructural Characteristics of Metals . . . . . . . . . . . . . . . . . . .1
Chapter 2 Chemical Compositions of Steel ......................... 41
Chapter 3 Physical Properties of Steel . . . . . . . .................... 63
Chapter4 Classification of Steel ................. . ............... 99

Part II Making, Casting and Rolling of Steel

Chapter 5 Primary and Secondary Steelmaking . . . . . . . . . . . . . . . . ...... 147
Chapter 6 Casting and Reheating of Steel ......................... 167
Chapter 7 Rolling Mills for Flat Products . . . . . . . . . . . . . . . . . . . . . . .193

Part Ill Deformation of Steel During Rolling

Chapter 8 Heat Transfer in Hot Rolling of Flat Products ............... 229
Chapter 9 Basic Principles of Macroscopic Plasticity ................... 245
Chapter 10 Theories of Flat Rolling . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
Chapter 11 Resistance to Deformation in Flat Rolling ................. 283

Part IV Metallurgical Aspects of Hot Rolling

Chapter 12 Structural Changes in Plain Carbon Steels During Hot Rolling .... 313
 CONTENTS

Chapter 13 Solubility and Precipitation of Microalloy Carbides/Nitrides .... 349

Chapter 14 Structural Changes in Microalloyed Steels During Hot Rolling .... 367
Chapter 15 Strengthening Mechanisms in Steels . . . . . . . . . . . . . . . . . . . 399
Chapter 16 Thermomechanical Treatment During Rolling and Cooling........ 419

Part V Properties of Flat Rolled Products

Chapter 17 Mechanical Properties of Hot Rolled Carbon Steels............. 44 7
Chapter 18 Cold-Forming and Fatigue Properties of Steels . . . . . . . . . . . . 461
Chapter 19 Metallurgical Defects in Cast Slabs and Hot Rolled Products .... 485

Part VI Plain and Microalloyed Carbon Steels

Chapter 20 Plain Carbon Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 513
Chapter21 Microalloyed Steels. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545
Chapter 22 Extra & Ultra Low Carbon Steels . . . . . . . . . . . . . . . . . . . . 581
Chapter 23 Multiphase Steels. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .601
Chapter 24 The Rolling Mill As a Metallurgical Device. . ................. 615

Nomenclature ..............................................627
Principal Works Consulted. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .643
Index ................... ...................... . ................... . 719
 Part I - Main Characteristics of Steel

Chapter 1

MICROSTRUCTURAL CHARACTERISTICS
OF METALS
1.1 Space Lattices
Substances can exist in either an amorphous or crystalline state. In the amorphous state, elemen-
tary particles are intermixed in a disorderly manner; their positions are not fixed relative to those of
their neighbors. In the crystalline state, this substance consists of atoms, or more properly ions,
which are arranged according to a regular geometric pattern that can vary from one substance to
another.

Body-centered cubic Face-centered cubic Close-packed hexagonal

Fig. 1.1 - Principal types of crystal lattices. Adapted from Higgins [1].

All metals are crystalline in nature. The crystallization of metals occurs during solidification
when the atoms of a liquid metal assemble themselves in an orderly arrangement and form a
definite space pattern known as a space lattice. There are several types oflattices in which metal-
lic atoms can arrange themselves upon solidification. The three most common crystal lattices are
shown in Fig. 1.1 and are known as [ 1]:

1
2 MICROSTRUCTURAL CHARACFERISTICS OF MEI'ALS

• Body-centered cubic (b.c.c.)

• Face-centered cubic (f.c.c.)
• Close-packed hexagonal (c.p.h.).

1.2 Lattice Constant

The side of an elementary cube or hexagon is known as a lattice constant (Fig. 1.2). These lengths
are usually expressed in Angstrom units (designated by symbols Aor A.U.) where one Angstrom
unit is equal to 1o-s centimeters. In metals, the length of the cube edge varies between 2.878 A in
chromium to 4.941 A in lead [2].

u c =Lattice constant

Fig. 1.2 - Lattice constant.

1.3 Metallic Bond

The term metallic bond is used to define the forces that hold the ions within a crystalline structure.
During the solidification of metals, the atoms relieve their outer (valence) electrons. As a result,
the atoms transform into ions which carry like positive charges and tend to repel each other.
However, the relieved valence electrons are donated to a common negatively charged electron
cloud, which is shared by all of the atoms that are present (Fig. 1.3). Thus, while the positively
charged ions repel each other, they are held in equilibrium positions by their mutual attraction to
the negatively charged electron cloud.

Positive ions . . . . . . • • •

. :_
•
e
~··-: .. ~.....--/
•

. . .. . . . . /
•
• • .. • • ~ Elecion cloud

. •••••••••
. . . . . .. .
.

Fig. 1.3- Diagrammatic representation of a metallic bond. Adapted from Higgins [1).

1.4 Allotropic Changes

When a metal undergoes a transformation from one crystal pattern to another, it is known as an
 MICROSTRUCTURAL CHARACTERISTICS OF METALS 3

allotropic change. The allotropic forms of iron are temperature dependent as illustrated in Table
1.1. When there is an allotropic change from a body-centered to a face-centered cubic lattice, it is
accompanied by a marked quantitative change in the characteristics and properties of the metal
involved. The allotropic change in the density of iron is shown in Fig. 1.4 [1,3].

Table 1.1 Allotropic forms of iron. Adapted from [3).

Crystallographic
I Temperature
Allotropic
Forms
I Forms Range

Alpha Body-centered cubic (b.c.c.) Up to 910°C (1670°F)

--- - - - -- - --- ---
Gamma Face-centered cubic (f.c.c.) 910- 1430°C (1670- 2557°F)
- - - -
Delta I Body-centered cubic (b.c.c.) 1403- 1535oC (2557- 2795°F)

12.6

12.4
<
l
~5 12.2
Delta ron
0
Q)
E
:g
::I
12.0

Gamma iron

800 1200 1600

Temperature, oc

Fig. 1.4- Allotropic changes in the density of iron. Adapted from Higgins [1 ).

1.5 Atomic Planes

Several sets of parallel planes can be drawn through a crystal so that all atoms constituting it would
be located in any one set. These are known as atomic planes.
Figure 1.5 illustrates the atomic planes in a cubic cell that is made up of eight atoms, with one
at each comer. The atomic planes are described by 3-digit numbers where each digit corresponds
to a unit coordinate in relation to the crystallographic axes X, Y, and Z. For example, the set of
planes designated by the symbol (001) would not cut either the X or theY axis [2].
4 MICROSTRUCTURAL CHARACTERISTICS OF METALS

(001) z z

y (010)
(110) z (101) z (011)
z
~

,;:: ~,.... I"" ~

"'
)
L.-
t7
y y

z (111)

Fig. 1.5- Atomic planes in a cubic cell. Adapted from Sauveur [2].

1.6 Crystallographic Anisotropy

The physical properties of a crystal depend on the direction of their measurement with respect to
their crystallographic axis. In the body-centered cubic crystalline structure of iron, the highest
strength lies in the direction of the atomic plane (111) and the lowest along the atomic plane (100)
as indicated in Fig. 1.6a.
Any deviation from a perfectly random orientation of the many crystals in a metallic material
will therefore result in anisotropy of the mechanical properties of the material [4]. The same can
be said with regard to the anisotropic character of the magnetic properties of some alloys such as a
silicon steel. The magnetic permeability of a silicon steel crystal is maximum when it is measured
along the atomic plane (100) and is minimum when measured along the atomic plane (111) as
shown in Fig. 1.6b [5].

1.7 Cooling Curve

A pure liquid metal solidifies into a crystalline solid at a fixed temperature called the freezing
 MICROSTRUCTURAL CHARACTERISTICS OF METALS 5

point (Fig. 1.7). This is due to the fact that the amount of internal heat relieved during·the crystal-
lization process is equal to the amount of heat given up by the material. The latter is known as the
latent heat of solidification [1].

(100)
Drection of lowest
strength

a) b)

Fig. 1.6 - Anisotropy of physical properties in a cubic crystal: a) mechanical strength,

b) magnetic permeability. Adapted from Roberts [4] and Bozorth [5].

Freezing begins Freezing ends

Uquid state Qystallization Sofld state

Time

Fig. 1.7- Typical cooling curve of a pure metal. Adapted from Higgins (1).

1.8 Metallic Dendrite

When a pure metal solidifies, each crystal begins to grow independently from a nucleus or center
of crystallization. The crystal develops by the addition of atoms according to the lattice pattern
evolving into what is called a dendrite as shown in Fig. 1.8. A metallic crystal grows in this way
because heat is dissipated more quickly from a point where the temperature decreases at the highest
rate leading to the formation of a rather elongated skeleton [ 1].

1.9 Dendrite Growth

The dendrite arms continue to grow and thicken (Figs. 1.9a, b) until ultimately the space between
them becomes completely solid. Meanwhile, the outer arms begin to make contact with those of
neighboring dendrites as shown in Fig. 1.9c. At this time, the dendrite growth ceases and solidifi-
6 MICROSTRUCI'URAL CHARACI'ERISTJCS OF METALS

cation is complete. The remaining liquid is used to thicken the existing dendrite arms leading to an
irregular overall shape of the crystals (Fig. 1.9d). An impure metal (Fig. 1.9e) carries the impuri-
ties between the dendrite arms, thus revealing the initial skeleton.

SecondlfY axis

TemlfY axis

~
Heat dissipation
and crystal ~wth

Fig. 1.8 - Early stages in the growth of a metallic dendrite.

a)

e)
Fig. 1.9- Dendrite growth of metallic crystals from liquid state. From Higgins [1].

1.1 0 Crystal Boundary

A solidified metal consists of a mass of separate crystals that are irregular in shape but interlocking
with each other like a three-dimensional jigsaw puzzle. It is now a widely held belief that a film of
 MICROSTRUCI'URAL CHARACTERISTICS OF METALS 7

metal about three atoms thick exists at the crystal boundaries, in which the atoms do not conform
to any pattern as illustrated in Fig. 1.10 [ 1,6].

Grain boundsy
(about 3 atoms thick)

Fig. 1.10- Diagrammatic representation of a grain boundary. Adapted from

Wusatowski [6] and Higgins [1].

1.11 Grain Shape and Size

The shape and size of the crystals depend on the cooling rate of the molten metal when it reaches
its freezing point. A slow decrease in temperature promotes the formation of relatively few nuclei,
resulting in a large crystal. Rapid cooling triggers the formation of a large number of nuclei
producing a large number of small crystals or grains (grain and crystal are used synonymously).
In a large ingot, the grain size may vary considerably from the outside surface to the center as
shown in Fig. 1.11. This is due to the variation in temperature gradient as the ingot solidifies and
the heat is transferred from the metal to a mold. It is possible to distinguish the following three
forms in the grain structure [ 1]:
• Small chill grains located at the surface of an ingot
• Columnar grains located in the intermediate zone
• Large equi-axed grains located at the center of an ingot.

1.12 Measurement of Grain Size

Prior to measurement of the grain size, a metallographic specimen has to be prepared in a manner
which reveals the relevant grain structure of the metal. There are three principal common methods
of grain size measurement [8]:
8 MICROSTRUCTURAL CHARACTERISTICS OF METALS

1. Comparator chart method

2. Heyn intercept method
3. Jeffries' planimetric method.

The details of these methods are described in ASTM Standard E112.

Equi-axed IT&ins Columnar grains

Chill IT&ins

Fig. 1.11 - Grain structure in a section of an ingot. Adapted from Higgins [1 ].

Comparator chart method - This method involves a comparison of the observed grain size
with a series of standard charts showing a range of different grain sizes. Each of grain sizes is
associated with an ASTM grain size number G. Figure 1.12 shows an example of an ASTM grain
size chart. The ASTM grain size number is an arbitrary exponential number G that refers to the
mean number of grains per square inch N at a magnification of x 100 diameters according to the
following equation [2, 7]:
N = 2G- 1 (1-1)

Thus, for an ASTM grain size of G = 1, there will be one grain per square inch as seen at a magni-
fication of x 100 diameters, or 1OOx 100 grains per square inch at a magnification of x 1 (real size).
Similarly, for an ASTM grain size of G = 8, there will be 128 grains per square inch as seen at a
magnification of x 100 diameters, or 120 x 104 grains per square inch at a magnification of x 1.
The Heyn intercept method - This method of evaluation of the grain size is most commonly
used whenever it is required to establish the quantitative relationships between the grain size and
mechanical or other properties of metals. The method involves counting the number of grain
boundaries intersected by a straight line of a given length imposed on a metallographic image. The
ASTM Standard E112 recommends to use the length of the intercept sufficient to include at least
50 grains. It is also recommended by this Standard, that for a non-equiaxed structure, the measure-
ments shall be made along the three principal axes of the specimen, longitudinal, transverse and
 MICROSTRUCIURAL CHARACIERISTICS OF METALS 9

normal. Alternatively, the circular intercepts shall be employed to produce an average intercept
length that could be useful for the prediction of grain boundary area per unit volume.

No.1 No. 2 No.3 No.4

up to 1.5 g-ains 1.5 to 3 g-ains 3 to 6 g-ains 6 to 12 g-ains

No. 5 No. 6 No.7 No.8

12 to 24 g-ains 24 to 48 grains 48 to 96 g-ains 96 IJ'ains and more

Fig. 1.12- ASTM grain size chart. Adapted From Johnson and Weeks [7].

Jeffries' planimetric method - This method is similar to the comparator method. However,
unlike to the comparator method that uses a derivative number for evaluation of the grain size, this
method defines directly the number of grains per square millimeter. According to this method, a
circle or rectangle of known area, usually 5000 mm2, imposed on micrograph or ground glass
screen. The magnification ofthe microscopic image is adjusted to give at least 50 grains within the
area. The number of grains intersected by the perimeter of the area are counted as half grains and
these are added to the grains contained entirely within the area.
The number of grains per square millimeter nA can be expressed by:
10 MICROSTRUCFURAL CHARACI'ERISTICS OF METALS

NM 2
n =-- (1-2)
A 5000

where
N = the number of grains counted
M = the linear magnification.

Table 1.2 Relationship between various types of presentation of the grain size. Abbreviated by
Gladman [8] from ASTM E112.

ASTM Nominal Fe ret Mean linear I Average area Calculated

grain size, diameter, diameter intercept of grain section number per unit
G d, (IJm) d1 (1Jm) i (IJm) a (1Jm 2) volume (mm·3)
- -
1 360 403 320 129,000 17.3
-
2 250 285 226 64,500 48.8
- -- -
3 180 202 160 32,300 138.0
- -- -- -
4 125 143 113 16,100 391

5 90 101 80 8,070 1,105

--
6 64 71 56.6 4,030 3,126
-
7 45 50 40.0 2,020 8,842
-----
8 32 36 28.3 1,008 25,010
-- --
9 16 18 14.1 252 200,000

10 11 13 10.0 126 566,000

I
11 8 8.9 7.1 63 1,600,000
-
12 5.6 6.3 5.0 31.5 4,527,000

13 : 4.0 I 4.5 3.5 15.8 12,800,000

--- - -
14 2.8 3.2 2.5 7.7 36,200,000

---1- Feret diameter

Reference direction
___ l__
Fig. 1.13 - Feret diameter of the polygonal planar intersection of a grain.
Adapted from Gladman [8].
 MICROSTRUCTURAL CHARACTERISTICS OF METALS 11

Three presentations of grain diameter are frequently used:

• Nominal grain diameter, dn

• Feret grain diameter, d1
• Mean linear grain intercept, i.

The nominal diameter dn is defined as the geometric mean of the mean linear intercept and the
Feret diameter, i.e.:

d, =g (1-3)

The Feret diameter d1 is defined as the distance between two parallel lines, tangential to
opposite edges ofthe grain section, that are parallel to the line of intersection used in measuring the
mean linear intercept as shown in Fig. 1.13.
The mean linear intercept i is derived from the average grain intercept area by assuming a
circular grain of average area, having a diameter d, so i = 1td/4.
Table 1.2 and Fig. 1.13 show the relationship between various types of presentation ofthe grain
SIZe.

1.13 Accuracy of Measurement of Grain Size

Accuracy of measurement of the grain size is directly related to the number of measured grains n.
It is convenient to express the error of measurement in relative terms [8]. Thus, the relative error
of the mean linear intercept i is equal to:

e1 = ( ~}100% ---
700
rn
(1-4)

where
ei relative error of the mean linear intercept, %
=
Ei = absolute error of the mean linear intercept.

Conversely, ifthe relative error of measurement e; is specified then the minimum number of the
intercepts required to achieve this accuracy can be calculated from the equation:

4900
n = =
2 (1-5)
et

Table 1.3 and Fig. 1.15 give the relationship between the minimum number of measured intercepts
n required to be within the relative error of measurement e; as calculated from Eq. (1-5).
12 MICROSTRUCIVRAL CHARACFERISTICS OF METALS

Table 1.3 Relationship between the minimum number of measured

intercepts n required to be within the relative error of measurement e..
Relative error, % ! 1.0 2.0 I 3.0 ~ 4.0
1

1
5.0
N~mb~of intercepts I 4900 1225 544 l -;; - 196 -

1.14 Phases in Metals

A phase is a distinct and physically, chemically, or crystallographically homogeneous portion of an
alloy. The following three solid phases are considered [2]:
• Pure metals
• Intermetallic compounds
• Solid solutions.

When an alloy contains more than one ofthese phases, it is generally referred to as an aggregate.

1.15 lntermetallic Compounds

Chemical compounds between metals and metalloids are known as intermetallic compounds.
Many of the known intermetallic compounds contain one of the following metalloids:
• Carbon (C)
• Phosphorus (P)
• Silicon (Si)
• Sulphur (S)
• Arsenic (As)
• Aluminum (Al) .

The important compound that is present in the alloys of iron and carbon is the carbide Fe3C or
cementite, which has an orthorhombic space lattice.

1.16 Solid Solutions

A complete merging in the solid state of the two phases, pure metals and intermetallic compounds,
is known as a solid solution. Solid solutions can consist of two metals, a metal and an inter-
metallic compound, or two compounds.
When a metal A forms a solid solution with another metal B that has a different space lattice,
the space lattice of the solid solution may either be similar to the lattice of one of the metals or
different from both. In the case where the lattice of the solution is identical to one of the metals, A
for example, that metal may logically be considered the solvent, and metal B the solute. If the
space lattice of the solution is unlike the lattice of either metal, the metal that is present in larger
proportions can be considered as the solvent.
There are two types of solid solutions that can be described as follows [2]:
 MICROSTRUCTURAL CHARACTERISTICS OF METALS 13

• Substitutional solid solution - A solid alloy in which the solute atoms replace some
atoms in the space lattice of the solvent as shown in Fig. 1.14a.
• Interstitial solid solution - A solid alloy in which the solute atoms are located at
random except at the lattice points within the space lattice as shown in Fig. 1.14b.

a) b)

e Positions of solvent atoms 0 Positions of solute atoms

Fig. 1.14- Space lattices of: a) substitutional solid solution, b) interstitial solid solution.

1.17 Phase Diagram

A phase diagram is a graphical representation of the temperature, pressure, and composition limits
of the phase fields in an alloy system as they exist under conditions of complete equilibrium.

Liquid solution

Solid solution

0 20 40 60 80 100
A 8
Percentage of 8

Fig. 1.15- Phase diagram of A-8 alloy. Adapted from Johnson and Weeks (7].

Phase diagrams are also known as equilibrium or constitutional diagrams. In a phase diagram
the temperature is plotted vertically while the composition is plotted horizontally. Any point on
14 MICROSTRUCTURAL CHARACTERISTICS OF MEI'ALS

the diagram represents a definite composition of a constituent and its temperature, with each value
being found by projecting to the proper reference axes. For illustration, Fig. 1.15 shows the
changes that take place during the cooling of an alloy that contains 50% element A and 50%
element B [7]. The alloy remains a homogeneous liquid solution until the temperature drops to the
value indicated by the intersection of the liquidus line at c0• The crystals which form from the 50-
50 liquid consist of a solid solution, the composition of which is found on the solidus line at c 1,
80% element B and 20% element A. As the mass cools, the composition of the growing crystals
changes along the solidus line from c 1 to c?, while the remaining liquid alloy varies in composition
along the liquidus line from c0 to c4 •
Figure 1.16 illustrates the iron-cementite phase diagram which is also known as the iron-
carbon phase diagram.

3000
1600
Molten alloy

1400
2500

1200

Austenite LL
Austenite, ledeburite, 0

and cementite
{
E
Alpha iron ~ gamma ron ~

600 in alpha ron

Perlite Perlite
"'C Cementite, peeriite,
and and
ferrite j .!!
'i cementite
and transformed ledeburite
w 8.
~

200

0~--._--~~--._--~----~--~----~--~~~~~
o.s 1.0 1.5 2.0 2.5 4.0
cnon,%

Fig. 1.16 - Iron-cementite phase diagram.

 MICROSTRUCI'URAL CHARACI'ERISTICS OF METALS 15

1.18 Definition of Constituents in Steel

Plain carbon steels are generally defined as the alloys of iron and carbon which contain up to 2%
carbon. For the present, we will neglect the effects of such elements as manganese which may be
present in most ordinary steels and also alloying elements which may be present in alloy steels, and
regard steels as being simple iron-carbon alloys.
Constituents in steels exist mainly as phases. They include molten alloy, delta ferrite, austenite
(gamma phase), ferrite (alpha phase), cementite and graphite. Another constituent in steels is
pearlite. It is not a phase but an aggregate [3].

1.19 Austenite
In iron-carbon alloys, austenite is the solid solution that is formed when carbon dissolves in face-
centered cubic (gamma) iron in amounts of up to 2%. The microstructure of austenite is usually
large grained as shown in Fig. 1.17.
Austenite is a difficult structure to retain at room temperature unless the steel contains a large
percentage of alloys, such as manganese or chromium. Austenitic steel is characterized by high
tensile strength and great ductility. The tensile strength is often around 125,000 lb/in. 2 with an
elongation in 2 in. of 35 to 40% [3,9].

Fig. 1.17 - Microstructure of austenite (Magnification: ~e500). From The

Making,Shaping and Treating of Steel [3]. Copyright AISE, Pittsburgh, PA. Re-
printed with permission.

1.20 Ferrite
In iron-carbon alloys, ferrite is a very dilute solid solution of carbon in a body-centered cubic
(alpha) iron and contains at most only 0.02% carbon. Figure 1.18 shows that the microstructure of
ferrite appears as polyhedral grains. Ferrite is very ductile and soft with a low tensile strength of
16 MICROSTRUCTURAL CHARACTERISTICS OF METALS

approximately 40,000 lb/in. 2 and an elongation in 2 in. of about 40% [3,9].

Fig. 1.18- Microstructure of ferrite (Magnification: x100) having a coarse grain size.
From The Making, Shaping and Treating of Steel [3]. Copyright AISE, Pittsburgh, PA.
Reprinted with permission.

1.21 Graphite
Graphite, or graphitic carbon is a free carbon in steel or cast iron where the carbon is amorphous,
having no particular form. Figure 1.19 illustrates the metallographic appearance of graphite in a
low-carbon steel that has been subjected to prolonged heating at a temperature below that at which
austenite is formed [3].

1.22 Cementite
Cementite, or iron carbide is an interstitial compound of iron and carbon with the approximate
chemical formula Fe3C that contains 6.69% carbon. When cementite occurs as a phase in steel, the
chemical composition is altered by the presence of manganese and other carbide-forming elements.
In the case of a slow cooled, relatively high-carbon steel, the microstructure of cementite
appears as a brilliant white network around the pearlite colonies or as needles interspersed with
pearlite as shown in Fig. 1.20a. Figure 1.20b shows the metallographic appearance of spheroidized
cementite in a steel which was heated to a temperature just below that at which austenite first
forms.
Cementite is a very hard compound with a tensile strength of approximately 5,000 lb/in. 2 and
an elongation in 2 in. that is equal to zero. Cementite is an unstable phase which over sufficient
time, decomposes into the two complete equilibrium constituents, iron and graphite [3,9] .
 MICROSTRUCIVRAL CHARACTERISTICS OF METALS 17

• ,
,,
·-
"

.: • •• •
..
- '
...
~.t
~
......
' ,. '

..
'~

•
• • " •

Fig. 1.19- Micrograph showing graphite particles in low carbon steel (Magnification:
x 100). From The Making, Shaping and Treating of Steel [3). Copyright AISE, Pittsburgh,
PA. Reprinted with permission.

a) b)

Fig. 1.20- Microstructures of (Magnification: x1000): a) slow-cooled high carbon steel showing pearlite
with cementite in the grain boundaries, b) spheroidized cementite in a matrix of ferrite. From The
Making, Shaping and Treating of Steel [3]. Copyright AISE, Pittsburgh, PA. Reprinted with permission.
18 MICROSTRUCI'URAL CHARACI'ERJSTJCS OF METALS

1.23 Pearlite
Pearlite is a lamellar aggregate of ferrite and cementite that is a result of the eutectoid reaction
which takes place when a plain carbon steel of approximately 0.08% carbon is cooled slowly from
the temperature range at which austenite is stable.

Fig. 1.21- Microstructure of pearlite (Magnification: x1000). From The Making, Shaping
and Treating of Steel [3). Copyright AISE, Pittsburgh, PA. Reprinted with permission.

Fig. 1.22- Microstructure of ledeburite (Magnification: x150). From The Making, Shaping and
Treating of Steel [3]. Copyright AISE, Pittsburgh, PA. Reprinted with permission.
 MICROSTRUCTURAL CHARACTERISTICS OF MEI'ALS 19

Figure 1.21 shows the lamellar micrographic structure ofpearlite that is known as the eutectoid
structure. Pearlite exerts the maximum hardening power of any constituent and has a tensile
strength of approximately 125,000 lb/in. 2 and an elongation in 2 in. of 10% [3,9].

1.24 Ledeburite
Ledeburite is an eutectic in the iron-carbon system, the constituents being an austenite and a
cementite. The eutectic contains 4.3% carbon. It is a constituent of iron-carbon alloys containing
more than 2% carbon and for this reason the dividing line between steels and cast iron is set at 2%
carbon. Fig.1.22 illustrates the microstructure of ledeburite in cast iron [3].

1.25 Transformation Temperature

The transformation temperature is the temperature at which a change in phase occurs and is also
known the critical point or critical temperature. The following symbols are used to define the
transformation temperatures in iron-carbon phase diagrams [9,10]:

Accm in hypereutectoid steel, critical temperature, at which the solution ofcementite in austenite
=
y is completed during heating
Ac1 critical temperature at which austenite y begins to form during heating
Ac3 = critical temperature at which transformation of ferrite a to austenite y is completed during
heating
Ac4 = critical temperature at which austenite y transforms to delta iron oduring heating
Ae1 = critical temperature in equilibrium diagram at which either austenite y begins to form
during heating, or austenite y transforms completely to ferrite a (or to ferrite a plus
cementite) during cooling
Ae temperatures of phase changes at equilibrium
Aecm = in hypereutectoid steel, critical temperature in equilibrium diagram, at which either the
solution of cementite in austenite y is completed during heating or precipitation of
cementite starts during cooling
Ae3 = critical temperature in equilibrium diagram corresponding to a complete transition either
from ferrite a to austenite yon heating or from austenite y to ferrite a on cooling
Ae4 = critical temperature in equilibrium diagram at which either austenite y transforms to delta
ferrite oduring heating or delta iron otransforms to austenite y during cooling
Arcm = in hypereutectoid steel, critical temperature, at which precipitation of cementite starts
during cooling
Ar1 = critical temperature at which transformation of austenite y to ferrite a (or to ferrite a plus
cementite) is completed during cooling
Ar3 = critical temperature at which austenite y begins to transform to ferrite a during cooling
Ar4 = critical temperature at which delta iron otransforms to austenite y during cooling.

Critical temperatures Ar1 and Ar3 decrease with the increase of cooling rates (Table 1.4).
20 MICROSTRUCI'URAL CHARACI'ERISTICS OF METALS

Table 1.4 Critical temperatures Ar1 ec) at various cooling rates (11].
Chemical composition, wt% ArJAr1 Cooling rate, °C/s
oc
c Mn Si p s AI Nb v 0.05 0.08 1.3 9.9

--
0.15 1.42 0.37 0.023 0.009 0.052 0.031 - Ar3 770 755 740
Ar1 650 635 -
0.15 1.39 0.39 0.016 0.009 0.039 0.046 0.046 Ar3 770 750 730 -
Ar, 645 635 620

1.26 Types of Multi-phase Reactions in Metals

The five multi-phase reactions in metals shown in Fig. 1.23 can be described as follows [12,13]:

Reaction Equation Phase Diagram

Eutectic L-+a+~
? ~
at +P
<p
Eutectoid y-+o:+~
? ~
0: +~
<p
1 <p
at+ p
Peritectoid
7v\
o:+~-+y

\ '\L
~
a. +L
Peritectic a+L-+~
(;\

~~
Monotectic Lt-+~+a.
/ at+Lz (a
Fig. 1.23 - Types of three-phase reactions in metals. Adapted from
Flemings [12].

Eutectic - Liquid solution L is converted into two or more solids a, ~ •... that are intimately
mixed on cooling.
Eutectoid - Solid solution y is converted into two or more intimately mixed solids a, ~ •...
 MICROSTRUCTURAL CHARACTERISTICS OF MEFALS 21

that are intimately mixed on cooling.

Peritectoid - Two or more solids ex, p, ... are converted into one solid y.
Peritectic - Solid ex reacts with liquid L to form a second solid p.
Monotectic - Liquid L 1 is converted into a solid ex and another liquid L2 •

1560 Delta ron

Molten alloy
1520

(.)
0

~e.· 1480
I
tE
Gl
I
I
1440
1-
I
Delta ron I
and austenite I Austenite
1400
I
I
I
1~~~----~~~~~----~~----~~----~~----._~----._~

0 0.10 0.20 0.30 0.40 0.50 0.60 0.70

Carbon,%

Fig. 1.24 - Phase diagram related to peritectic steel. Adapted from Porter and Easterling [13).

1.27 Phases in Peritectic Steel

Peritectic steel is a plain carbon steel having a carbon content of approximately 0.065 to 0.17%.
Figure 1.24 shows that when the temperature of liquid peritectic steel is greater than 1495°C
(2723°F), it crystallizes into delta iron. At temperatures below 1495°C, the liquid reacts with solid
delta iron to form a second solid phase that is gamma iron.
After the reaction begins, the gamma iron separates the two reacting phases. During this
process, the atoms of these two reacting phases diffuse through solid gamma iron. Since diffusion
through a solid is very slow, a segregated microstructure containing both the delta and gamma iron
is produced [12]. Segregation during a peritectic reaction can lead to longitudinal cracking during
casting of steels, especially when casting thin slabs.

1.28 Phases in Hypoeutectoid Steel

Hypoeutectoid steels are steels that contain less than the eutectoid percentage of carbon which is
approximately 0.80% in plain carbon steel. At some temperature above Ae3, a steel containing
22 MICROSTRUCTURAL CHARACTERISTICS OF METALS

0.40% carbon is completely austenitic as shown in Fig 1.25a. On slow cooling below Ae3, the
austenite first rejects ferrite which concentrates at the grain boundaries (Fig. 1.25b).
As the temperature falls down to Ae1, the crystals of austenite shrink as shown in Fig. 1.25c and
their carbon content increases to 0.80%. On cooling below Ae1, the austenite changes to pearlite so
that the final constituents in steels below Ae 1 are ferrite and pearlite as illustrated in Fig. 1.25d [1].

500 ~--~~--~----~----_. _____._____.____ ~----~

0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

c.t>on,%

Fig. 1.25- Phase transformation in steel containing 0.4% carbon. Adapted from Higgins [1].

1.29 Phases in Eutectoid Steel

Eutectoid steel contains the eutectoid percentage of carbon which is nearly 0.80% in plain carbon
steels. Eutectoid steel does not begin to transform from austenite (Fig. 1.26a) on cooling until the
critical temperatureAe 1_3 is reached. The transformation then begins and ends at the same tempera-
ture (723°C or 1333°F), and the final structure is entirely pearlite as shown in Fig. 1.26b [1].

1.30 Phases in Hypereutectoid Steel

Hypereutectoid steels are steels containing more than the eutectoid percentage of carbon which is
approximately 0.80% in plain carbon steels. At some temperature above Aecm, a steel containing
1.2% carbon is completely austenitic as shown in Fig. 1.27a. On slow cooling below Aecm, the
carbon will precipitate as needle-shaped crystals of cementite around the austenite grain boundaries
(Fig. 1.27b,c).
 MICROSTRUCI'URAL CHARACI'ERISTICS OF METALS 23
1100.--------------------------------------------,
Austenite
Ferrite
1000 ; Cementite
Peaiite

900
(.)
0

ef
.aIll
800
l Austenite + Cementite

!
700 Ferrite
Ae 1 Ae1-3

600 Ferrite + Peaiite

Peaiite + Cementite

0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

Carbon.%
Fig. 1.26- Phase transformation in steel containing 0.8% carbon. Adapted from Higgins [1].

1100 .-------------------------------------------~
Austenite
Ferrite
1000 Cementite
Peaiite

900
(.)
0
Austenite

700

600
Ferritl!l
Ae1

Ferrite + Peaiite
•.
,
~ ~ e) :

cf Peaiite + Cementite

0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

c.bon,%

Fig. 1.27- Phase transformation in steel containing 1.2% carbon. Adapted from Higgins [1).
24 MICROSTRUCTURAL CHARACTERISTICS OF MEIALS

As a result the carbon content in an austenite will be gradually reduced down to 0.80% at the
temperature Ae 1_3• Below this point, the remainin'g austenite will then transform to pearlite as
shown in Fig. 1.27d [1].

1700 t-----1~--+---4---.....f...---1---~
G
• AD, andP/1 900
• Other data

860
0
0

780

740

-·
1300 ......__.......,._ _ PI, _ _.,__~1---4- tv, """'"---1 700
0 0.2 0.4 0.6 0.8 1.0 1.2
Cerbon,%
Fig. 1.28- Phase transformation temperature in steels. Adapted from Krauss [14]

1.31 Phase Transformation Hysteresis

Phase transformations do not occur at the same temperature in heating as in cooling [ 10,14]. The
meta] is rather reluctant to change its physical state so that in heating, the Ac temperatures are
somewhat higher than equilibrium temperatures Ae.
Likewise, the Ar temperatures on cooling are lower than equilibrium temperatures Ae as shown
in Fig. 1.28. The difference in temperature between the Ac and the Ar can vary in some cases as
much as 24°C or 75°F.

1.32 Supercooling of Austenite

As previously shown, austenite transforms to pearlite when it is cooled slowly below the Ar critical
temperature. When austenite is more rapidly cooled, however, this transformation is retarded. As
the cooling rate is increased, the transformation temperature is lowered which results in the forma-
tion of the micro-constituents that are shown in Table 1.5 [3].
The following symbols are used to define the transformation temperatures of austenite to
martensite [1 0]:
 MICROSTRUCI'URAL CHARACTERISTICS OF METALS 25

Ms = Temperature at which transformation of austenite to martensite starts during cooling

Mr = Temperature at which martensite formation finishes during cooling
Mn = Temperature at which the microstructure will consist of n% martensite and (1-n)%
retained austenite.

Table 1.5 Constituents formed during supercooling of austenite. Adapted from

The Making, Shaping and Treating of Steel [3).

Constituents Temperature Range

Pearlite 705 to 535"C (1300 to 1OOO"F)

- - - -f- ~

Bainite 535 to 230"C (1000 to 450"F)

1-- - - - - t- - -
Martensite Below 230"C (450"F)

According to Andrews [ 11 ], the critical temperature Ms can be expressed as a function of steel

chemical composition expressed in wt%, as given by the equations:

M11(DC) = 539-423[q-30.4[Mn]-ll[SJ1-17.7[Nl1-12.1[Cr]-7.5[Mo] (1-6)

M 11(DC) = 512-453[q+217[q2 -71.5[q[Mn]-67.6[q[Cr] (1-7)

+ 15[Cr] -16.9[Ni] -9.5[Mo]

The last equation takes into account the interactions between alloy elements.

1.33 Bainite
Bainite is a decomposition of austenite consisting of an aggregate of ferrite and carbide. Figure
1.29 shows the appearance of bainite as feather like if formed in the upper part of the temperature
range and acicular if formed in the lower part. The hardness of bainite increases as the transforma-
tion temperature decreases due to the finer distribution of carbide that forms at lower temperatures.
In a given steel, the bainitic microstructure will generally be found to be both harder and
tougher than pearlite, although the hardness will be lower than that of martensite [3].

1.34 Martensite
Martensite is an interstitial supersaturated solid solution of carbon in iron having a body-centered
tetragonal lattice. It is a metastable phase of steel that is formed by the transformation of austenite
below the M5 temperature.
Transformation to martensite occurs almost instantly during cooling and the percentage of
transformation is dependent only on the finish cooling temperature. Martensite is the hardest of the
transfonnation products of austenite. It has either acicular or needlelike microstructure.
26 MICROSTRUCTURAL CHARACTERISTICS OF METALS

Fig. 1.29- Electron micrograph (Magnification: x15,000) of bainitic microstructure formed on complete
transformation of eutectoid steel at 260"C (500"F). From The Making, Shaping and Treating of Steel [3].
Copyright AISE, Pittsburgh, PA. Reprinted with permission.

Fig. 1.30- Electron micrograph (Magnification: x15,000) of the structure of tempered martensite at a
tempering temperature of 595"C (1100"F). From The Making, Shaping and Treating of Steel (3).
Copyright AISE, Pittsburgh, PA. Reprinted with permission.
 MICROSTRUCTURAL CHARACTERISTICS OF METALS 27

Figure 1.30 shows the microstructure ofthe so called tempered martensite, which is formed when
martensite is reheated to a subcritical temperature after quenching [3].

1.35 Isothermal Transformation Diagrams

Isothermal transformation diagrams, or Time-Temperature-Transformation (T.T.T.) curves are
shown in Fig. 1.31 and can be constructed by completing the following five steps [1,3]:
a) Heating a number of similar specimens of steel to just above the Ac1 temperature
b) Quenching these specimens to a different temperature in an incubation liquid bath
c) Holding the specimens in the bath during predetermined time intervals
d) Final quenching of the specimens in water
e) Examining the microstructure to reveal the extent to which the phase transformation
had taken place at the holding temperature.

Stable austenite
-- 723°C-------------
700

600

500

(.) 400

si.
0
Acicular

E - · M. - - - - - - - - - - - - - - - - - -
~ 200

100
Austenite + Mnnsite

0
- MF ___ - - - - - - - - - - - - - - -
-100
Martensite

10 100 1000
Time, s (logarithmic scale)

Fig. 1.31 - Time-Temperature-Transformation (T.T.T.) curves for plain carbon

steel of eutectoid composition. Adapted from Higgins [1].
28 MICROSTRUCTURAL CHARACFERISTICS OF MEI'ALS

1.36 Continuous-Cooling Transformation Diagrams

Continuous-cooling transformation diagrams reveal the phase transformations that occur during
continuous cooling of a selected specimen at a predetermined constant cooling rate [1]. The
continuous-cooling diagram lies below and to the right of corresponding isothermal diagram as
shown in Fig. 1.32 in application to a plain carbon steel of eutectoid composition.
Curves A, B, and D represent cooling rates of approximately 5, 400, and 50°C per second
respectively. For example, in the case of curveD, transformation would begin at P with a forma-
tion of some fine pearlite. Transformation, however, is interrupted at Q and does not begin again
until the M, temperature is reached at R. Curve C represents the critical cooling rate which is the
minimal cooling rate that must be maintained to obtain a completely martensitic microstructure.

I
0

E
~

100 - - Cooling diagram

- · - Constant-me cooling c~
Ow-------~------~----~~------._
0.1 10 100
___________
1000 10000
nne, s (logarithmic scale)

Fig. 1.32- The relationship between T.T.T. and continuous cooling curves.
Adapted from Higgins [1).

1.37 Types of Heat Treatment

Heat treatment is the process of heating a solid metal or alloy to a certain temperature as shown in
Figs. 1.33 and 1.34. This heating is then followed by subsequent cooling at a specific rate in order
to obtain the desired conditions or properties. Table 1.6 shows the major types of heat treatment
processes and the resulting microstructures of the finished product [3,14].
The main purposes of annealing are to relieve the cooling stresses that are induced .during hot
and cold working along with softening the metal to improve its machinability or formability. The
 MICROSTRUCTURAL CHARACTERISTICS OF METALS 29

annealing process also produces a uniform microstructure of ferrite and pearlite [14].

"C "F
1600 2912

1500 2732

1400 2552

1300 2372

!e 1200 2192
Acm
2012
1100
e8. 1000 1832
~
900 1652

800 1472

700 1292

600 1112
0 0.5 1.0 1.5 2.0
Carbon content in weight percent

Fig. 1.33- Portion of the Fe-C diagram showing temperature ranges for full annealing, normalizing,
hot working and homogenizing. From Principles of Heat Treatment of Steel, by G. Krauss [14], ASM
International, 1980. With permission.

Table 1.6 Microstructures produced by major heat treatment processes.

Adapted from Krauss [14] and Makin':/, Shaping and Treating of Steel [3].
Heat Treatment
Microstructure
Process

Full annealing Ferrite and pearlite

Isothermal annealing Ferrite and pearlite

Normalizing Ferrite and pearlite

l -
I
Spheroidizing Ferrite and carbide
- - - -- - I
- -
Quenching and tempering Tempered martensite
-

Martempering Tempered martensite

- -

Austempering Bainite
~ ·
-- f- -

Dual-phase Ferrite and martensite

1.38 Full Annealing

Full annealing produces a coarse pearlite microstructure in low or medium-carbon steels. The
30 MICROSTRUCTURAL CHARACTERISTICS OF METALS

process consists of heating at a relatively high temperature in the austenitic region so that a full
carbide solution is obtained. This is followed by slow cooling which produces a complete transfor-
mation in the high-temperature end ofthe pearlite range as shown in Fig. 1.35. Though the process
is considered to be simple and reliable for most steels, it is rather slow and requires a significant
amount of time to cool the material from the austenizing temperature to room temperature
"C "F
1100 , . . . - - - - - - - - - - - - - - - . . . . , . . . . . - , 2012

1000 1832

1652

j
900

800

e8. 700
~
600

500 932

400 ........_._...._..........................J 752

L....o__.__._...._..__.__.._._~......_..._.

0 0.5 1.0 1.5 2.0

Carbon content in weight percent
Fig. 1.34 - Portion of the Fe-C diagram showing temperature ranges for process
annealing, recrystallization annealing, stress relieving and spheroidizing. From
Principles of Heat Treatment of Steel, by G. Krauss [14], ASM International, 1980.
With permission.

CONVENTIONAL ANNEALING

PRODUCT: FERRITE 8 PEARLITE

TIME - LOG SCALE

Fig. 1.35- Schematic transformation diagram for full annealing. From The Mak-
ing, Shaping and Treating of Steel, 1985 [3). Copyright AISE, Pittsburgh, PA.
Reprinted with permission.
 MICROSTRUCTVRAL CHARACTERISTICS OF MEFALS 31

ISOTHERMAL ANNEALING

TIME- LOG SCALE

Fig. 1.36 - Schematic transformation diagram for isothermal annealing. From

The Making, Shaping and Treating of Steel, 1985 [3). Copyright AISE, Pittsburgh,
PA. Reprinted with permission.

1.39 Isothermal Annealing

The isothermal annealing process provides a coarse pearlite microstructure on the material and has
a considerable time savings when compared with the time required by full annealing [3]. Isother-
mal annealing is achieved by rapid cooling ofthe material from the austenizing temperature to the
transformation temperature. This temperature is then maintained until the transformation is
complete and the material is then rapidly cooled to room temperature as shown in Fig. 1.36. If the
extreme softness of the coarse pearlite is not necessary, the transformation may be carried out at a
nose of the curve, which allows for a further speedup of the annealing process.
Isothermal annealing is utilized in a continuous heat treatment process commonly known as
cycle annealing. The cycle annealing furnace is equipped with an air-blast chamber for rapid
cooling from the high austenizing temperature down to the holding temperature at which the
isothermal transformation to pearlite occurs.

1.40 Normalizing
Normalizing is a heat treatment process that is similar to full annealing and having a main objec-
tive of producing a uniform microstructure of ferrite and pearlite. Another objective of normaliz-
ing is to refine the grain size, which frequently becomes very coarse during hot working or is
present in steel casting [3,14].
32 MICROSTRUCTURAL CHARACTERISTICS OF MEI'ALS

Normalizing in hypoeutectoid steels is performed at temperatures that are higher than those
used for annealing. Hypereutectoid steels are heated above the temperature Acm as was shown in
Fig.l.33. Figure 1.37 shows that for both hypoeutectoid and hypereutectoid steels, heating is
followed by air cooling, which provides a much faster cooling rate in comparison with that of full
annealing. As the cooling rate increases, the temperature range over which ferrite and pearlite are
being formed is lowered, resulting in a more refined microstructure of the product. Consequently,
the product would have higher strength and hardness along with lower ductility.

Heating cyclel Cooling cycle

t
t
Normalize:

AcJ
Ac1

...:I
G)

......as
8.
E
~

Time

Fig. 1.37 - Schematic time-temperature cycles for normalizing and full annealing.
From Principles of Heat Treatment of Steel, by G. Krauss [14], ASM International,
1980. With permission.

.........as
Q)

:I

8.
E
~

Ferrite
and
carbide

Time

Fig. 1.38 - Schematic heat treatment cycle for spheroidizing an air-hardening

steel. Martensite forms first and then is tempered close to the Ac1 temperature to
produce a spheroidized structure. From Principles of Heat Treatment of Steel, by
G. Krauss [14], ASM International, 1980. With permission.
 MICROSTRUCI'URAL CHARACI'ERISTICS OF METALS 33

1.41 Spheroidizing
Spheroidized microstructures in steels consist of spherical carbide particles that are uniformly
dispersed in a ferrite matrix as shown in Fig. 1.20b. The spheroidized microstructure is the most
stable microstructure in steels and provides for improved ductility, which is important for low and
medium-carbon steels. This type of microstructure is also used to obtain a lower hardness, which
is important for high-carbon steels that undergo machining prior to final hardening [3,14].
Spheroidizing can be accompanied by either complete or partial austenizing with a subsequent
holding just above the critical temperature Act and then cooling very slowly through the Act (Fig.
1.38}, or cycling above and below Act. Spheroidizing of martensite microstructures is frequently
performed on highly alloyed tool steels that form martensite on air cooling.

1.42 Homogenizing
Homogenizing is a type of annealing treatment that is usually performed in the earlier stages of
steel processing prior to hot rolling or forging [15]. The main purpose of homogenizing is to
obtain uniformity or homogeneity of austenite, which improves the hot workability and helps the
product to obtain a uniform microstructure during subsequent annealing or hardening operations.
Homogenizing is usually performed at high temperatures in the austenitic phase field as shown
in Fig. 1.33, to speed up the reduction of segregation or chemical concentrations that are produced
during the solidification of an ingot or slab. At these high temperatures, second phases such as
carbides are also most fully dissolved.

1.43 Stress Relieving

The primary purpose of stress relieving is to relieve stresses that have been introduced to a work-
piece from hot and cold working processes or welding. The stress relief is accomplished by
recovery mechanisms that precede recrystallization. Steel is stress relieved by heating the work-
piece to a temperature below the lower critical temperature A 1 (Fig. 1.34). The holding time at this
temperature must be sufficient to reduce the residual stresses to an acceptable level. This is then
followed by cooling at a relatively slow rate to avoid the creation of new stresses [14].
Some steels exhibit a loss of toughness on slow cooling from temperatures of approximately
535°C (1000°F) and above. To avoid this phenomenon which is known as temper brittleness,
rapid cooling is utilized.

1.44 Quenching and Tempering

Quenching and tempering is the heat treatment commonly used to obtain a tempered martensite
microstructure which is characterized by relatively high toughness and good ductility [3]. During
quenching, a workpiece is heated to a temperature at which austenite is formed and then cooled
rapidly so that transformation does not occur at the temperature above the martensite range. Water,
oils or brine are the most commonly used medium for quenching.
The formation of hard and brittle martensite is accompanied by the creation of a high residual
stress. Tempering, which is similar to stress relieving, can relieve these stresses and also improve
34 M!CROSTRUCIVRAL CHARACTERISTICS OF MEIALS

ductility. The tempering operation should immediately follow quenching in order to minimize
cracking as shown in Fig. 1.39.

CUSTOMARY QUENCHING
AND TEMPERING

TIME- LOG SCALE

Fig. 1.39 - Schematic transformation diagram for quenching and tempenng. From
The Making, Shaping and Treating of Steel, 1985 [3]. Copyright AISE, Pittsburgh, PA.
Reprinted with permission.

MARTEMPERING

PROOUCT: TEMPERED MARTENSITE

Tl ME - LOG SCALE

Fig. 1.40 - Schematic transformation diagram for martempering. From The Making,
Shaping and Treating of Steel, 1985 [3]. Copyright AISE, Pittsburgh, PA. Reprinted
with permission.
 MICROSTRUCTURAL CHARACFERISTICS OF MEFALS 35

1.45 Martempering
Martempering is a modified quenching procedure that is used to reduce the high residual stresses
which are usually created during the rapid cooling through the martensite temperature range [3].
This heat treatment is carried out by quenching a workpiece into a molten-salt bath at a tempera-
ture just above the martensite transformation temperature M 5 • The workpiece is held in this bath to
establish a constant temperature throughout the workpiece and then air cooled to room
temperature. As a result, the transformation to martensite occurs during the relatively slow air
cooling process. After martempering, the workpiece can then be tempered to the desired hardness
as shown in Fig. 1.40. Tools, bearings, and dies are examples of the types ofworkpieces that are
usually subjected to martempering.

1.46 Austempering
Austempering is a heat treatment that is used to obtain a lower bainite microstructure which is
similar in strength and superior in ductility to those of tempered martensite [3]. This heat treat-
ment includes quenching to the desired temperature in the lower bainite region, usually in a
molten-salt bath and holding the workpiece at this temperature until the transformation to bainite is
completed (Fig. 1.41 ). After austempering, the workpiece is either quenched or air cooled to room
temperature. The workpiece can also be tempered to a lower hardness level if required.
A major advantage of this process over conventional quenching and tempering is minimum
distortion and the absence of quench cracking. Plain high-carbon steels in small section sizes, such
as sheet, strip, and wire are typical products for austempering.

AUSTEMPERING

"'
a:
::1
~
a:
"'
IL
.......2

PRODUCT: BAINITE

Tl ME - LOG SCALE

Fig. 1.41- Schematic transformation diagram for austempering. From The Mak-
ing, Shaping and Treating of Steel, 1985 [3]. Copyright AISE, Pittsburgh, PA.
Reprinted with permission.
36 MICROSTRUCTURAL CHARACTERISTICS OF METALS

1.47 Dual-Phase Heat Treatment

The main purpose of dual-phase heat treatment is to obtain a microstructure that represents a
mixture of ferrite and martensite by heating the steel into the intercritical temperature region
(between the A 1 and A3 temperature). In this region, the microstructure consists of ferrite and
austenite. Since the austenite area of steel in this region is high in carbon, the steel has a higher
ability to form martensite during quenching than a steel that was heated above the A3 temperature.
The amount of martensite that forms during dual-phase heat treatment depends on the cooling
rate. lntercritical continuous annealing allows low-carbon hot or cold-rolled sheet steel to obtain a
dual-phase microstructure consisting of ferrite with 15 to 20% martensite. Sheets with this dual-
phase microstructure also have increased strength and superior ductility.

1.48 Surface Hardening

Surface hardening is a heat treatment process that is utilized to obtain a hard, wear-resistant surface
along with a strong, fracture-resistant core. The two most common surface hardening processes are
decremental hardening and case hardening [3].
Decremental hardening - This is the process of increasing the surface hardness without a
change in the chemical composition of the surface. This can be achieved by heating the workpiece
at a high rate in order to produce a steep temperature gradient. This heating is continued until the
A3 temperature is reached at the desired depth below the surface at which time the workpiece is
then quenched. Decremental hardening can be accomplished by one of the following processes:
• Heating in a furnace that is maintained at high temperature
• Flame hardening or direct impingement of a high temperature
• Induction hardening which utilizes induction heating.

Case hardening- This is the process that involves a change in the chemical composition of the
surface portion of a workpiece. Variations of this process such as carburizing, nitriding, and
carbonitriding can be utilized as follows:
• Carburizing produces a high-carbon layer at the surface of low-carbon steel by heating
it in contact with either carbonaceous solid material or in a carbon-rich liquid (liquid
carburizing) with subsequent quenching. Depending on the process, the heating tem-
perature varies from 870°C to 1050°C (1600°F to 1920°F).
• Nitriding introduces nitrogen into the surface layer of a solid ferrous alloy by holding it
in contact with nitrogen material. For ferritic steel, the holding temperature is below
theAc 1 temperature and quenching is not usually required. The gas-phase nitronization
treatment is known as bright annealing.
• Carbonitriding combines both carburizing and nitriding processes .

1.49 Aging Processes in Steel

Aging is a process of gradual change in steel properties with time. There are two principal aging
 MICROSTRUCI'URAL CHARACI'ERISTICS OF METALS 37

processes in steel [3]:

• Quench aging
• Strain aging.

Quench aging - In application to carbon steel, quench aging can be described as a process of
gradual change in steel properties with time after quenching. Quench aging is caused by the
precipitation of carbon, nitrogen, or both from supersaturated solid solution in ferrite. These two
elements occupy interstitial positions in the alpha-iron lattice. Their solubility decreases sharply
with decrease in temperature. In carbon steels, carbon C is the principal agent in quench aging.
After rapid cooling, it can precipitate at ambient or slightly elevated temperatures in the form
of finely dispersed particles of iron carbide. This produces significant changes of the steel proper-
ties, including [3,16]:

a) increased hardness
b) increased yield strength
c) increased tensile strength
d) decreased elongation
e) decreased reduction area in tension test
f) increased transition temperature from ductile to brittle fracture in a notch-impact test
g) increase in coercive magnetic force
h) decrease in magnetic permeability.

Fig. 1.42 - Changes in hardness of 0.06% carbon steel quenched from no•c
(1325"F) after aging at indicated temperatures. From Metals Handbook, Aging of Iron
and Steel, 1948 [16]. Copyright ASM International. Reprinted with permission.

Figure 1.42 shows that hardness increases more rapidly when aging occurs above room temper-
ature, but a higher absolute value of hardness is attained by aging at room temperature. Aging for
periods beyond that corresponding to the maximum hardness results in decrease in hardness. This
phenomenon is known as overaging. In order to reduce quench aging, the carbon and nitrogen
38 MICROSTRUCTURAL CHARACTERISTICS OF MEIALS

content in supersaturated solid solutions must be minimized by cooling the steel slowly, especially
through the temperature range from 540°C to 315°C (1 000°F to 600°F). Another method is to
form stable carbides and nitrides by adding alloys to the steel such as titanium or zirconium.
Strain aging- Strain aging differs from quench aging in several ways [3]:

a) plastic deformation must precede the aging process

b) supersaturated solution of carbon and nitrogen is not essential for aging; although if it is
present, the rate and extend of stain aging will be enhanced
c) nitrogen rather than carbon is mainly responsible for strain aging in steels
d) there is little or no overaging.

Strain aging is caused by the segregation of interstitial solute atoms of carbon, nitrogen to the
strain fields of dislocations in the alpha-iron lattice. This disrupts the regular periodicity of the
lattice and enlarges the interstitial sites. Subsequently, because the dislocations become 'frozen' in
place, it would require a higher stress to produce the same amount of plastic deformation. Most of
the effects of strain aging on properties of steels are similar to those of quench aging. There is,
however, another unwelcome characteristic of strain aging, related to the abrupt yield point elonga-
tion characteristic of the temper rolled low-carbon steels.
Caused by strain aging, this phenomenon leads to appearance of so called Liider strain lines
after subsequent deformation. Strain aging can occur during the tension test that is conducted
oc
within the temperature range from 150 to 350 °C (from 302 °F to 662 °F). This phenomenon is
known as dynamic strain aging, or blue brittleness. Strain aging is commonly minimized by
removal of nitrogen N. This is frequently accomplished, for instance, by adding aluminum AI to
the steel, so about 0.05% of aluminum is retained in the product, forming aluminum nitride (AlN).

References
1. Higgins, R.A., Engineering Metallurgy, Part 1, Applied Physical Metallurgy, Robert E.
Krieger Publishing Company, Melbourne, Fla., 1983.

2. Sauveur, A., The Metallography and Heat Treatment of Iron and Steel, Fourth Edition,
McGraw-Hill Book Company Inc., New York and London, 1935.

3. The Making, Shaping and Treating ofSteel, 1Oth edition, Eds. Lankford, W.T. et al, Associa-
tion oflron and Steel Engineers, Pittsburgh, PA, 1985.

4. Roberts, W.L., Cold Rolling ofSteel, Marcel Dekker, Inc., New York, 1978.

5. Bozorth, R.M., Fe"omagnetism, D. Van Nostrand Company, Inc., Toronto, 1951.

6. Wusatowski, Z., Fundamentals ofRolling, Pergamon Press, Oxford, 1969.

7. Johnson, C.G. and Weeks, W.R., Metallurgy, Fifth Edition, American Technical Society,
 MICROSTRUCTURAL CHARACTERISTICS OF METALS 39

Chicago, 1977.

8. Gladman, T., The Physical Metallurgy of Microalloyed Steels, The Institute of Materials,
London, UK, 1997.

9. Keller, J.F., Lectures on Steel and Its Heat Treatment, Evangelical Press, Cleveland, Ohio,
1928.

10. Avner, S.H., Introduction to Physical Metallurgy, Second Edition, McGraw-Hill Book
Company, New York, 1974.

11. Andrews, K.W., "Empirical Formulae for the Calculation of Some Transformation Tempera-
tures," Journal of the Iron and Steel Institute, Vol. 203, 1965, pp. 721-727.

12. Flemings, M.C., Solidification Processing, McGraw-Hill, New York, 1974.

13. Porter, D.A. and Easterling, K.E., Phase Transformations in Metals and Alloys, Second
Edition, Chapman & Hall, London, 1992.

14. Krauss, G., Principles ofHeat Treatment ofSteel, ASM International, Materials Park, Ohio,
1980.

15. Pickering, F.B., Physical Metallurgy and the Design of Steels, Applied Science Publishers,
London, 1978, pp. 1-88.

16. Metals Handbook, ASM International, Materials Park, Ohio, 1948, p. 439.
 Chapter 2

CHEMICAL COMPOSITIONS
OF STEEL

2.1 Major Effects of Alloying Elements

Steel by definition is an alloy of iron that contains 0.03 to 1. 7% carbon along with various alloying
elements that are added to obtain specific properties. Steel can be generally divided into the
following two groups [ 1]:
a) Low alloy steels containing less than 5% elements other than iron
b) High alloy steels containing more than 5% elements other than iron.

Alloying elements and impurities are incorporated into austenite, ferrite and cementite. If the
alloy or impurity atoms are nearly the same size as the iron atoms, the iron atoms are usually
replaced. If these atoms are significantly smaller than iron atoms, such as nitrogen, the incorpora-
tion may occur by filling in the interstitial sites. In cases when solubility levels are exceeded, other
phases than those in plain carbon steel may form. A typical example is the combination of the
cementite structure M3C (M represents a combination of chromium and iron atoms), that forms
when small amounts of chromium are added to iron-carbon alloys at 890°C (1634°F). Larger
amounts of chromium cause the carbides M 7C3 and M 23 C6 to be formed [2]. Depending on their
effect on the formation and stabilization of phases in steels, the alloying elements are usually
considered as [3,4]:
• Austenite formers
• Ferrite formers
• Carbide formers.

2.2 Austenite Formers

Austenite formers are the alloying elements which enlarge the austenite field. The following

41
42 CHEMICAL COMPOSmONS OF STEEL

elements are considered as austenite formers [4]:

• Carbon (C)
• Cobalt (Co)
• Copper (Cu)
• Manganese (Mn)
• Nickel (Ni)
• Nitrogen (N) .

Figure 2.1 illustrates the typical effect of an austenite former on the austenitic field.

I
/ ~ ....
2600
1-' r--.... ...... - I400
.......
2400 I 300

--
~--- ........
...........
.....,
2200 I
29"Y
. 5~
• .., I
~2000 4"Y·~
t; 6. 5~,~ ~/
i 1800
.~,

~
~,

~ /035"f.Mn
.....-::
~ . 5"f.Mn
~K
1600

1400
t'::
,........_ ~~"Y.Mn~ 800
~ Carbon steel, 0.35 "f. Mn

1200
~ t--- ~ 100
\ ~ \6.5 •t. Mn 600
J'<3"Y.Mn
0 .2 0 .4 0 .6 0.8 1.0 1.2 1.4 1.6 1.8
Carbon,%

Fig. 2.1 - Effect of several uniform manganese contents on the carbon limitations
for pure austenite at elevated temperatures. From Alloying Elements in Steel, by
Bain, E.C. and Paxton, H.W., Second Edition [3]. Copyright ASM International.
Reprinted with permission.

2.3 Ferrite Formers

Ferrite formers are alloying elements that enlarge the ferrite field as shown in Fig. 2.2 which uses
chromium as the alloying element. The following elements are considered ferrite formers [4] :
• Aluminum (Al)
• Chromium (Cr)
• Niobium (Nb)
• Molybdenum (Mo)
• Phosphorus (P)
• Silicon (Si)
• Titanium (Ti)
• Tin (Sn)
 CHEMICAL COMPOSITIONS OF STEEL 43

• Tungsten (W)
• Vanadium (V).

2800
-I 500
2600
/ ......
io-' ......
~~ -I 400
... ...
v 111 ~ V . . ....
/
2400
v ~
I 300

~-2200
.... r-...... u
•;;
I
1200!
1
Er"~~. f""""'...
r>
I
:.
t:7
v
I 'Y....
i2ooo 1100~
I , ,. •
1000!
l Cr ,,
~ 1800
12%
/ Cr -1"% ,
,,'
1600 ~
~ ./ Cr 900
.....
.... , , ..
~

./ ~;:'\
Carbon 11111, 0% Cr 800
1400
........ 700
1200

0 .2 0 .4 0.6 0 .8 1.0 1.2 1.4 1.6 1.8

Carbon, 'Y.

Fig. 2.2 - Effect of several uniform chromium contents on the carbon limitations
for pure austenite at elevated temperatures. From Alloying Elements in Steel, by
Bain, E.C. and Paxton, H.W ., Second Edition [3). Copyright ASM International.
Reprinted with permission.

2.4 Carbide Formers

Elements such as chromium, tungsten, vanadium, molybdenum, titanium, and niobium fonn very
stable carbides when added to steel as shown in Fig. 2.3. These additional elements generally
increase the hardness of steel, particularly when the carbides fonned are harder than iron carbide
[5]. Other elements, such as manganese are not strong carbide fonners, however, they do contrib-
ute to the stability of the other carbides that are present.

2.5 Effect of Alloying on Microstructure

When several elements are present in a steel, their combined effect with respect to the fonnation of
austenite can be described by the Austenite Stabilizing Equivalent (ASE) and by the Ferrite
Stabilizing Equivalent (FSE) which are equal to [5]:

ASE = [Ni] + 30[C] + 0.5[Mn] + 12[N] (2-1)

FSE = [Cr] + [Mo] + l.5[Si] + 2[Nb] + 3[Ti] (2-2)

44 CHEMICAL COMPOSITIONS OF STEEL

Proportion Present Also Present

Element
as Carbide In Steel as

Nickel

Silicon

Aluminum Nitrides

Manganese MnS inclusions

Chromium

Tungsten

Molybdenum

Vanadium Nitrides

Titanium Nitrides

Niobium

Copper Sol. 0.3% max Cu globules if> 0.3%

Lead Pb

Fig. 2.3 - Physical states in which the principal alloying elements exist in steel.
From Engineering Metallurgy, Part 1, by Higgins, R.A., 1983 [5). Reprinted with
permission.

The symbols in Eqs. (2-1) and (2-2) represent the weight percent ofthe element indicated. By
using ASE and FSE as the coordinates in a modified Schaefjler diagram as shown in Fig. 2.4, it is
possible to define the microstructure of alloyed steel after air-cooling from its austenite conditions.

2.6 Effect of Alloying on Critical Temperatures

The effect of alloying elements on the critical temperatures can be illustrated by the following
empirical formulas which were developed by Andrews [6] and Shiga, et al [7]. These formulas are
based on statistical analysis of experimental data:

Ac3 eC) = 910- 203{[q- 15.2[Nz1 + 44.7[Sz1 + 104[VJ + 31.5 [Mo] +

(2-3}
+ 13.1 [Wj- 30[Mn]- 11 [Cr]- 20[Cu] + 700[P] + 120[As]

Ac1 COC) =723- 10.7[Mn]- 16.9[Nz1 + 29.1 [Si] + 16.9[Cr] + 290[As] + 6.38[Wj (2-4)
 CHEMICAL COMPOSITIONS OF STEEL 45

Ar3 eC) = 910- 273 [C]- 14[Mn]- 57[Nz]- 16[Cr]- 9[Mo]- 5[Cu] (2-5)

M,eC) = 539-423 [C]- 30.4[Mn] -11 [Si] -17.7[Nz]-12.1 [Cr] -1.5 [Mo] (2-6)

M,eC) = 512-453 [C] + 217 [C] 2 -71.5 [C] [Mn]- 67.6 [C] [Cr]
(2-7)
+ 15 [Cr] -16.9 [Nz]- 9.5 [Mo]

In the above formulas, the symbols represent the weight percent of the element indicated.
The formulas are applicable for steel containing less than 0.6% C and less than 5% of each of the
other alloying elements. The last equation takes into account the interactions between alloy
elements.

z~ 25
Austenite

Martensite

0 5 10 15 20
Ferrite stabHizing equivalent
(%Cr + %Mo + 1.5 x %Si + 2 x %Nb + 3 x %TI)

Fig. 2.4 - Modified Schaeffler diagram. From Engineering Metallurgy, Part 1, by Higgins,
R.A., 1983 [5]. Reprinted with permission.

The addition of all alloying elements, with the exception of cobalt, results in retardation of the
46 CHEMICAL COMPOSITIONS OF STEEL

transformation rates at temperatures between 500°C (932°F) and 700°C (1292°F). Therefore, the
effect of alloying reduces the critical cooling rate that is necessary to obtain martensite [5].

2.7 Effect of Alloying on Eutectoid Composition and Temperature

When alloying elements are added to carbon steel, the solubility of carbon in austenite diminishes
[3]. An alloy steel will be completely pearlitic if it contains less than 0.8% carbon. As shown in
Fig. 2.5, the addition of manganese and nickel lowers the eutectoid temperature, whereas the other
elements cause this temperature to rise [3].
2400

2200

Mol l/w'
v
Ti Vsi
2000
~
~j
f ) I
"'
~1800
•
r ~ ~ ~
/
v
!!1600
v
~
'U Cr ~ ~
..
2u
~ j...--- ~

-
~1400
I~""'

....._
--......;:: r---

r--=::: r--
1200
~ t--...
1000 ~ .. .........
- -........... .....

2 4 6 8 10 12 14 18
Alloyinu element. "Y.

Fig. 2.5 - Eutectoid composition and eutectoid temperature as influenced by several

alloying elements. From Alloying Elements in Steel, by Bain, E.C. and Paxton, H.W.,
Second Edition [3). Copyright ASM International. Reprinted with permission.

2.8 Effect of Alloying on Hardenability

The effect of alloying elements on hardenability can be evaluated by the hardenability multiplying
factor as shown in Fig. 2.6. This factor is derived by measuring the hardenability of a series of
steels in which a single alloying element is the only variable [4].
It was found that the cumulative hardenability he of an alloy steel that contained more than one
alloying element can be calculated as follows:
 CHEMICAL COMPOSITIONS OF STEEL 47

(2-8)

where
h8 = hardenability of base iron-carbon alloy
K 1, K2, Kn = hardenability multiplying factors of alloying elements .

3.5
8.0

3.0
~ 7.0
§ ~
I:J)
2.5 j
c
2-
I:J)
6.0 c
:8- 2-
3 Q.
:e
:::E :::I
2.0 :::E
5.0

1.5
4.0

2.0 4.0
Alloying element %
Fig. 2.6 - Hardenability multiplying factors for a variety of alloying elements. Adapted
from The Making, Shaping and Treating of Steel [4).

,,
/si jJn
240
:p
220
v ,.
. ....
I
I
1 / ,

LI
200

~~
I

1
lL v
Ill 180

~Vv
XI
c
Ni,
" ../"_

L " "" ~ v ,• "

v v
'E
as 160

-
.c
~

I v,' "" ~ ~ v
_1 / ........
~ 140
~ v
I-- ~
f...--
120

100
rjj ," ~ .........:::: ~ v
~ r--
f-""
- -
r-'
rv,~ ~ r---- ~
80 ~- - - -

0 2 4 6 8 10 12 14 16 18 20 22
Alloying element, %

Fig. 2. 7 - Probable hardening effects of the various elements as dissolved in pure

iron. From Alloying Elements in Steel, by Bain, E.C. and Paxton, H.W ., Second
Edition [3). Copyright ASM International. Reprinted with permission.
48 CHEMICAL COMPOSITIONS OF STEEL

2.9 Effect of Alloying on Hardness

Alloying elements contribute to the hardness in steel by being either carbide formers or ferrite
strengtheners [4]. The carbide-forming elements, such as chromium, molybdenum, and vanadium
greatly affect tempering behavior. These elements raise the tempering temperature that is required
to obtain a given hardness.
The ferrite strengtheners increase the hardness of ferrite by forming solid solutions. This
furnishes a method of increasing the hardness of steel in the unhardened state as shown in Fig. 2. 7.
This hardening effect is small when compared to that obtained by changes in the dispersion of the
carbide.

2.10 Effect of Alloying on Tensile Strength

As in the case of hardness, the ferrite strengthening effect on tensile strength is small when
compared with that obtained by changes in the dispersion of carbides.

2.0
I
I
1.8
c I
J Mn
Mo If
1.6

i r/ I .
Cu,-'
,.
LL.

1.4
v ,
.,

l j_ .j Si
• I

p
J
/} V.'
'Q- --- ----
Ni-
~u ,.~_, v
1.2
v

1.0
~~
0 1.0 2.0 3.0
Alloying &Iemen~ %

Fig. 2.8 - Walters' factors for estimating tensile strength of pearlitic steels in the
normalized condition. From Engineering Metallurgy, Part 1, by Higgins, R.A., 1983
[5]. Reprinted with permission.

An increase in tensile strength as a function of the content of the principal alloying elements
can be estimated by using the multiplication factors derived in application to pearlitic steels in the
normalized condition [5], as shown in Fig. 2.8. The multiplication factor equal to 1 corresponds to
a pure iron with a tensile strength of 250 N/mm2 (36,000 psi). The most accurate results are
obtained for steels with less than 0.25% carbon and within the intermediate alloy range.
 CHEMICAL COMPOSITIONS OF STEEL 49

2.11 Effect of Alloying on Grain Growth

The presence of some elements, notably chromium, results in an increased rate of grain growth in
steel. In the case of overheating the steel, it can promote brittleness which is usually associated
with coarse grain [5]. The opposite effect or retardation of grain growth is produced by vanadium,
titanium, niobium, aluminum, and to some degree, nickel.
Vanadium, titanium and niobium inhibit the grain growth by forming finely-dispersed carbides
and nitrides that are relatively insoluble at high temperatures and act as barriers to grain growth.
The carbides of tungsten and molybdenum that are present in high-alloy tool steels reduce grain
growth at heat-treatment temperatures. Aluminum that is present in aluminum-killed steel makes
it inherently fine-grained.

2.12 Effect of Alloying on Corrosion-Resistance

The addition of elements such as aluminum, silicon, and chromium results in substantial improve-
ment of corrosion resistance. These elements form a thin but dense film of oxide that adheres to
the surface of the steel and protects it from further attack [5]. Chromium is the most effective
element when corrosion resistance at high temperatures is required.

2.13 Effect of Alloying on Electrical Resistance

In general, the addition of most alloying elements, with the exception of copper (Cu), increases the
electrical resistance of steel [8]. As follows from Fig. 2.9, the most effective contributors to
electrical resistance are carbon (C), silicon (Si), aluminum (Al), and tin (Sn). An increase in the
content of molybdenum (Mo) and cobalt (Co) (up to approximately 9%) produces an increase in
electrical resistivity, whereas any further additions ofthese alloying elements result in a decrease of
electrical resistivity.

2.14 Residual Elements and Impurities

Residual elements are elements which are present in an alloy in small quantities, but not added
intentionally [4,9]. The most common residual elements and their main sources are as follows:
• Hydrogen, oxygen, and nitrogen may be introduced during the steelmaking process.
• Nickel, copper, molybdenum, chromium, and tin may be transferred to steel from scrap.
• Aluminum, titanium, vanadium and zirconium may be introduced during the
deoxidation process.

Impurities are elements or compounds whose presence in a material is undesired. Nonmetallic

substances in a solid metallic matrix are often referred to as inclusions [8]. Impurities can be
present in steel in both solid and gaseous forms and either as pure elements or oxides.
Nitrogen, hydrogen, carbon monoxide, and oxygen are typical gaseous impurities that can be
found in steel in a dissolved state, as gas bubbles, or a combination of both. The main effect of
gaseous impurities is a decrease in plasticity. Hydrogen also causes embrittlement of steel.
50 CHEMICAL COMPOSITIONS OF STEEL

100
CHANGE 0' SCALE

~
~
.
..
.~ 80
'E
uI
E
&:.
e
·e
u
60
.....
CX)
ID
0
... 40
.::
-;;
·;;;
!
0u
u..
·.:
iij

0
0 4 8 10 20
Alloyino element, •1.

Fig. 2.9 - Effect of alloying elements on electrical resistance of iron. From

Metals Handbook, Eighth Edition, Vol. 1, 1961[8). Copyright ASM Interna-
tional. Reprinted with permission.

Residual elements such as nickel, copper, molybdenum, chromium, and tin increase the
hardenability of carbon steels and may also change the heat-treating characteristics. In some
applications where ductility is important, this increased hardness can be harmful.
Carbon, sulphur, nitrogen and oxygen are especially harmful in electrical sheet steels because
they occupy interstitial spaces in the crystal structure and, even in small amounts, can cause
significant deterioration ofthe magnetic properties of these steels [10].
Iron oxide is another type of impurity that is formed during the steelmaking process and can be
trapped in solid steel during solidification. These impurities are known as dirt. Oxides which
remain in steel are mechanically mixed with it, breaking up the continuity of the steel structure and
disrupting the directional uniformity of the physical properties of steel. These oxides can also
serve as points of weaknesses from which a fracture may commence.

2.15 Carbon (C)

Carbon is often called the Master because of its influence on the properties of steel. Although by
itself, carbon does not possess strength or hardness, in solid solutions such as iron carbide (Fe3C),
it is the chief controller of strength and hardness as shown in Fig. 2.1 0. The principal functions of
carbon are [ 1]:
 CHEMICAL COMPOSIDONS OF STEEL 51

• Increase strength, hardness, and hardenability

• Lower ductility, malleability, magnetic characteristics, and electrical conductivity.

180 90

300

270

240

2101
cii

180 =
~
I
150

120

10 90

Fig. 2.10 - Approximate influence of carbon content on tensile properties of carbon

steel in the as-rolled condition (section thickness approx. 0.50 to 0.75 in.). From
Alloying Elements in Steel, by Baln, E. C. and Paxton, H.W ., Second Edition (3).
Copyright ASM International. Reprinted with permission.

The range of carbon content in various types of steel is shown in Table 2.1 [9].

Table 2.1 Carbon content of various types of steel (9].

Type of Steel Carbon Content (~•)

Plain carbon steels 0.03 - 1.04

High-speed tool steels 0.75 - 1.60

-
Hot-work tool steels 0.22 - 0.70

Cold-work tool steels 0.45 - 2.85

52 CHEMICAL COMPOSmONS OF STEEL

2.16 Manganese (Mn)

Manganese is widely used in steel production for deoxidation and desulphurization of molten steel.
Manganese remains in steel in an amount less than 1%, but when its content exceeds 1%, it is
regarded as a deliberate alloying element. The principal functions of manganese as an alloying
element are as follows [3,5]:
• Increase tensile strength as shown in Fig. 2.11.
• Moderately increase hardenability and promote both toughness and machinability.
• Minimize the resulting hot and cold brittleness (shortness) in steels containing sulphur.

120,000~~

0.70

0 .60

0.50
it
g040
...
&>
0
u
0 .30

020

0 .10

0 0 .20 0 .40 0 .60 0.80 1.0

Mon9oneu, "•

Fig. 2.11 - Approximate carbon and manganese compositions required to pro-

duce the indicated tensile strengths (in psi) in as-rolled steel. From Alloying
Elements in Steel, by Bain, E.C. and Paxton, H.W., Second Edition [3). Copyright
ASM International. Reprinted with permission.

The range of manganese content in various types of steel is shown in Table 2.2 [9].

Table 2.2 Manganese content of various types of steel [9].

Type of Steel Manganese Content (%)

Plain carbon steel 0.25 - 1.65

- I
Manganese steel I 1.60 - 1.90
- -
I
Cold-work tool steels 0.30- 2.50
--
Chromium-nickel austenitic
stainless steel
2.00 - 15.50
 CHEMICAL COMPOSITIONS OF STEEL 53

2.17 Molybdenum (Mo)

Molybdenum is a strong carbide former that forms the hard, stable carbide Mo2C as well as the
double carbides such as Fe4Mo 2C and Fe21 MoC 6 • The principal functions of molybdenum as an
alloying element are as follows [5]:
• Small amounts of molybdenum effectively reduce transformation rates displacing the
nose of the time-temperature-transformation (T.T.T.) curve to the right.
• Raises high-temperature strength and creep resistance of high-temperature alloys.
• Enhances corrosion resistance of stainless alloys particularly in chloride solutions.
• Replaces much of the tungsten in high-speed tool steels.
• An addition of approximately 0.3% molybdenum is usually sufficient to reduce the
tendency to produce temper-brittleness in low-nickel, low-chromium steels.
• One of the important components of nickel-chrome-moly steels that combine high
tensile strength with good ductility.
• Improves machinability and mechanical properties in chromium steels.
• Enhances case-hardening in nickel-molybdenum steels.

The range of molybdenum content in various types of steel is shown in Table 2.3 [9].

Table 2.3 Molybdenum content of various types of steel [9].

Type of Steel Molybdenum Content ("'o)

Molybdenum steel 0.15 - 0.60

- --
Tool steel:
High-speed steel I 0 - 10.00
Hot-work steel 0- 5.50
Cold-work steel 0 - 1.80
1-- - - ---- --
Stainless steel:
Austenitic chromium-nickel steel 0 - 4.00
Martensitic chromium steel 0 - 1.25
Ferritic chromium steel 0 - 1.25

2.18 Chromium (Cr)

Chromium is a carbide former that forms the hard carbides Cr7C3 or Cr23 C6 or, alternatively, double
carbides with iron. All of these carbides are harder than ordinary cementite. As a ferrite former,
chromium lowers the A 4 temperature and raises the A 3 temperature thereby stabilizing the alpha-
phase at the expense of gamma-phase. If more than 11% chromium is added to a pure iron, the
gamma-phase is entirely eliminated. The principal functions of chromium as an alloying element
are as follows [3,5]:
• Increases the hardness of steels when a sufficient amount of carbon is present. Low-
chromium steels containing 1.0% carbon are extremely hard.
• Increases strength with some loss of ductility in low-carbon steels .
54 CHEMICAL COMPOSITIONS OF STEEL

• Contributes to high-temperature strength.

• Provides moderate contribution to hardenability.
• Improves abrasion resistance in high-carbon steels.
• Improves corrosion resistance due to the protective layer of oxide that forms on the
surface when added in large amounts (up to 25%).
• Promotes grain growth resulting in increased brittleness of steel.

The range of chromium content in various types of steel is shown in Table 2.4 [9].

Table 2.4 Chromium content of various types of steel [9].

I
Type of Steel Chromium Content

Chromium steel 0.30 - 1.60

- - -
I
- --·
Stainless steel:
Austenitic chromium-nickel steel 15.0 - 30.0
Martensitic chromium steel 4.0 - 18.0
Ferritic chromium steel 10.5 - 27.0
Precipitation hardening steel 12.2 - 18.0
f-- - - - - -+- - --- --· -

Heat-resistant casting alloys:

Nickel-base alloys 0 - 21.0
Cobalt-base alloys 0 - 27.0

2.19 Nickel (Ni)

Nickel does not form carbides and its presence in steel makes iron carbides less stable and there-
fore promotes graphitization. Nickel acts as a ferrite strengthener by forming a simple
substitutional solid solution. As an austenite former, nickel stabilizes austenite by raising the A4
temperature and depressing the A3 temperature. If more than 25% nickel is added to pure iron, the
resulting alloy becomes purely austenitic even after slow cooling to ambient temperatures. The
principal functions of nickel as an alloying element are as follows [3,5]:
• Increases strength and toughness in alloy steels with a nickel content up to 5%.
• Makes high-chromium composition austenitic just as in chromium-nickel austenitic
stainless steels.
• Induces the grain-refining effect.
• Substantially increases thermal hysteresis of the allotropic transformation in high-nickel
steels that contain small amounts of carbon, so that martensite can be retained in steels
as it occurs in martensite aging (maraging) steels after heating up to 600°C (lll2°F).
• Reduces the coefficient of thermal expansion.
• Increases the magnetic permeability in high-nickel alloys.

The range of nickel content in various types of steel is shown in Table 2.5 [9].
 CHEMICAL COMPOSITIONS OF STEEL 55

Table 2.5 Nickel content of various types of steel [9].

Type of Steel Nickel Content (%)

l
Nickel steel
-
_ _l 3.25- 5.25
--
Stainless steel:
Austenitic chromium-nickel steel 1.00 - 37.00
Martensitic chromium steel 0 - 2.50
Precipi~tion hardening steel 3.00 - 8.50
r-
Heat-resistant casting alloys:
Nickel-base alloys 50.0- 75.0
Cobalt-base alloys 0 - 27.0

2.20 Vanadium (V)

Vanadium is a strong carbide former that forms the carbide VC. Vanadium is present in the
microstructure as finely dispersed carbides and nitrides that are not dissolved at normal heat-
treatment temperatures, but their presence produces a barrier to grain growth. A sufficient amount
of carbon and vanadium soluble at elevated temperatures causes the maximum observed secondary
hardness effects. The principal functions of vanadium as an alloying element are as follows [3,5]:
• Restricts austenitic growth and is a very important grain refiner. As little as 0.1% vana-
dium effectively restricts grain growth during the hardening processes. Grain growth,
however, starts immediately after the steel is heated to the temperature at which the
grain-growth restricting particles of carbide and nitride dissolve.
• Promotes hardenability even when dissolved in small amounts.
• Induces resistance to softening at high temperature.
• Readily combines with oxygen and nitrogen and is often used as a scavenger or
cleanser in the final stage of deoxidation to produce a gas-free ingot.
• Chromium-vanadium steels show higher yield stress and percentage reduction in area.

The range of vanadium content in various types of steel is shown in Table 2.6 [9].

Table 2.6 Vanadium content of various types of steel [9].

Type of Steel Vanadium Content (%)

Chromium-vanadium steel 0.10 - 5.25

Tool steel:
High-speed steel 0.90- 5.25
Hot-work steel 0- 2.20
Cold-work steel 0 - 5.15

2.21 Tungsten (W)

Tungsten is a very strong carbide fonner that fonns the extremely hard and stable carbides W2C,
56 CHEMICAL COMPOSITIONS OF STEEL

WC, and the double carbide Fe4 WzC. These carbides dissolve very slowly and only at very high
temperatures. Therefore, tungsten is an important constituent of tool steels and particularly high-
speed tool steels. In these steels, a substantial increase in hardness can be achieved after secondary
hardening. As a ferrite former, tungsten lowers the A4 temperature and raises the A3 temperature.
The principal functions of tungsten as an alloying element are as follows [3,5]:
• Inhibits grain growth and therefore has a grain refining effect.
• Reduces decarburization during hot working and heat treatment processes.
• Induces abrasion resistance.
• Develops high-temperature (red) hardness in quenched and tempered steels.
• Contributes to creep strength in some high-temperature alloys.
• Contributes considerably to hardenability.
• Opposes softening in tempering where steels containing tungsten can be heated in the
range 600-700°C (1112-1292°F) before carbides begin to precipitate resulting in soften-
ing the steel.

The range of tungsten content in various carbon and tool steels is shown in Table 2.7 [9) .

Table 2. 7 Tungsten content of various carbon and tool steels [9).

I
Type of Steel Tungsten Content (%)

Tungsten-chromium steel 1.75 (nom.)

- - -
Tool steel:
High-speed steel 1.15 - 21 .0
Hot-work steel 0 - 19.0
Cold-work steel I 0- 2.0
Shock-resisting steel 0- 3.0

2.22 Cobalt (Co)

Cobalt is a carbide former with a carbide-forming tendency that is slightly stronger than that of
iron. Cobalt is an essential added constituent of selected tool steels, superalloys, and permanent-
magnet alloys.
In some alloys containing 18% nickel, 8 to 12% cobalt, 3 to 5% molybdenum and small
amounts oftitanium and aluminum, cobalt enhances the precipitation hardening process by produc-
ing more sites for nucleation of (Ti, AI, Mo )Ni 3 precipitates. In these alloys, the original iron-
nickel martensite contributes about one half of the strength whereas the other half is due to subse-
quent precipitation hardening. The latter process is known as aging of martensite and therefore
these alloys are referred to as maraging steels. The principal functions of cobalt as an alloying
element are as follows [3,5]:

• Promotes high residual induction and high coercive force in permanent-magnet alloys.
• Enhances high strength and considerable toughness by stimulating the precipitation
hardening process.
 CHEMICAL COMPOSITIONS OF STEEL 57

• Resists softening with an elevation in temperature when dissolved in ferrite or aus-

tenite.
• Provides a negative contribution to hardenability.

The range of cobalt content in various steels and superalloys is shown in Table 2.8 [9].

Table 2.8 Cobalt content of various steels and superalloys [9].

Type of Steel I Cobalt Content (o/o)

Tool steel:
High-speed steel 0 - 13.0
Hot-work steel 0- 4.5
- - - -- - - r-
Heat-resistant casting alloys:
Nickel-base alloys
Cobalt-base alloys
l1 0 - 18.5
42.0 - 67.5

2.23 Aluminum (AI)

Aluminum has a carbide-forming tendency that is less than that of iron and also promotes graph-
itization. The principal functions of aluminum as an alloying element are as follows [3] :
• Restricts grain growth by forming an effective fine dispersion with nitrogen or oxygen.
• Forms an effective surface-hardening layer by relatively low-temperature diffusion of
nitrogen (nitriding).
• Restricts corrosion by forming a strong layer of aluminum oxide on the steel surface.
• Acts as an excellent deoxidizer.
• Contributes moderately to hardenability.

The ranges of aluminum content in various steels and alloys is shown in Table 2.9 [9].

Table 2.9 Aluminum content of various steels and alloys [9).

Type of Steel Aluminum Content (0/o)

Ferritic stainless steel 0 - 0.30

Precipitation-hardening stainless
steel
0 - 1.50
- -
Heat-resistant casting alloys: I
Nickel-base alloys 0- 6.5
Cobalt-base alloys 0- 4.3

2.24 Titanium (Ti)

Titanium is an extremely strong carbide former. The principal functions of titanium as an alloying
element are as follows [3,5]:
58 CHEMICAL COMPOSITIONS OF STEEL

• Withdraws carbon from solution and reduces martensitic hardness and hardenability in
medium-chromium steels.
• Prevents formation of austenite in high-chromium steels.
• Withdraws carbon from solution in austenitic stainless steels at elevated temperatures
and thereby prevents intergranular deterioration as a result of the chromium-carbide
formation at the grain boundaries with accompanied depletion of local chromium.
• Promotes precipitation hardening in austenitic high-temperature alloys.
• Contributes to malleability in killed high-strength low-alloy steels by making improve-
ments in inclusion characteristics, mainly by rounding the sulphides. The same effect
can be achieved by utilizing zirconium and rare earths.
• Used as a deoxidizer.

The range oftitanium content in various steels and alloys is shown in Table 2.10 [9].

Table 2.10 Titanium content of various steels and alloys [9].

Type of Steel Titanium Content

1

High-strength low-allow sheet steel I 0 - 0.1 0

-~
Heat-resistant casting alloys:
Nickel-base alloys 0- 5.0
Cobalt-base alloys 0- 3.8

2.25 Silicon (Si)

Silicon is a ferrite former that raises both A1 and A3 temperatures. Since silicon has a graphitizing
effect, it is usually combined in steels with manganese as a carbide stabilizer. The principal
functions of silicon as an alloying e]ement are as follows [3,5]:
• Raises magnetic permeability and electrical resistivity in electrical sheet steels and
allows one to obtain very low magnetic hysteresis losses. The silicon content range in
these steels is between 0.5 and 4.5%.
• Contributes to oxidation resistance in some heat-resistant steels .
• Increases hardenability, strength, and impact toughness when combined with manga-
nese.

2.26 Copper (Cu)

Copper, is an austenite former. Since copper has a graphitizing effect, it is added to low-carbon
steels only, and in quantities not greater than 1.5%. The principal functions of copper as an
alloying element are as follows [5]:
• Improves corrosion resistance .
• Produces an alloy with increased tensile strength obtained by precipitation hardening .
 CHEMICAL COMPOSITIONS OF STEEL 59

• Produces a rather small increase in yield strength in steels that are not precipitation
hardened.
• Increases hardenability in carbon steels that may result in reduced ductility.

2.27 Lead (Pb)

Lead has limited solubility in molten steel. Since lead has a much greater density than steel, it
settles in molten steel leading to a heavy lead segregation. Lead is also present in steel in an
elemental form as small inclusions that are soft and act as internal lubricants. It is also an impor-
tant constituent of leaded steels that are used for making tools [4,9].

2.28 Boron (B)

Boron is a very hard solid which melts at 2300°C (4172°F) and is added to steels known as boron
steels. The principal functions ofboron as an alloying element are as follows [5] :
• Hardenability of fully-deoxidized steels increases when very small amounts of boron
(from 0.0005 to 0.005%) are added due to the reduction in phase transformation rates
during cooling. This effect is most useful in low-carbon steels.
• Addition of small quantities of boron allows one to reduce the amounts of other more
expensive alloying elements by as much as one-half while maintaining the same trans-
formation rates.
• Improves malleability and machinability in steels.

2.29 Niobium (Nb)

Niobium (also known as columbium) provides strengthening by both precipitation hardening and
ferrite grain refinement. Niobium is an important constituent of some high-strength low-alloy
sheet steels. The principal functions of niobium as an alloying element are as follows [4]:
• Small quantities of niobium (approximately 0.02%) significantly increase the tensile
strength and yield strength of carbon steels.
• Increase in strength is accompanied by a marked deterioration of notch toughness that
can be avoided by special rolling practices involving lower-than-normal temperatures
for the last rolling passes.

2.30 Sulphur (S)

Sulphur produces the most harmful effect on steel quality by forming the brittle sulphide FeS.
When s'ulphide is present in steel in quantities as low as 0.01 %, it may trigger a precipitation of the
sulphide at the crystal boundaries as shown in Fig. 2.12a. The principal functions of sulphur as an
alloying element are as follows [5]:
• Forms brittle sulphides that have a low melting point causing steel to crumble during
hot working. The steel also becomes unsuitable for cold-working processes.
60 CHEMICAL COMPOSITIONS OF STEEL

• When a sufficient amount of manganese is added to steel, sulphur fonns manganese

sulphides MnS which are plastic at hot-working temperatures. These sulphides are
distributed throughout the steel as rather large globules (Fig. 2.12b) that are not soluble
in steel and thus not associated with the steel structure.

a) b) c)

Fig. 2.12 -a) Segregation of iron sulphide (FeS) at crystal boundaries of steel (Magnification:
750x), b) Formation of isolated manganese sulphide (MnS) globules when manganese is
present in steel (Magnification: 200x), c) Ghost bands or areas lacking in pearlite which
indicates the presence of phosphorus (Magnification: x75). From Engineering Metallurgy, Part
1, by Higgins, R.A., 1983 [5]. Reprinted with permission.

2.31 Phosphorus (P)

Phosphorus dissolves in solid steel when in quantities of less than 1%. When this amount is
exceeded, phosphorus precipitates in the form of the brittle phosphide Fe3P. The principal func-
tions of phosphorus as an alloying element are as follows [5]:
• Produces a significant hardening effect in solution. However, its amount is usually
limited to 0.05% due to an increase in brittleness. This is especially true in the pres-
ence of the phosphide Fe3P as a separate constituent in the microstructure.
• Forms so-called ghost bands in hot rolled or forged steel, which are areas containing no
pearlite but with a high concentration ofphosphorus (Fig. 2.12c). These areas become
the planes of weakness in steel.

2.32 Nitrogen (N)

In steel, nitrogen either forms nitrides or remains dissolved interstitially after solidification. In
both these forms, nitrogen causes steel to be brittle and unsuitable for severe cold work [5].
Therefore, in order to produce mild steel with high ductility, the nitrogen content must be kept as
low as 6.002%. This reduction in nitrogen content also reduces quench aging.

2.33 Hydrogen (H)

Hydrogen contents of more than about 0.0005% will result in reduced ductility of steel. Hydrogen
can be diffused out of steel at room temperature, but this diffusion is more effective at slightly
 CHEMICAL COMPOSITIONS OF STEEL 61

elevated temperatures [4]. Hydrogen, in excess of0.0005%, also contributes to internal cracking
which usually occurs during the cooling of a metal after rolling or forging.

2.34 Tin (Sn)

Tin adversely affects hot workability. Its another drawback arises from the fact that it is less easily
oxidized than iron. Specifically, on slab reheating in an oxidizing atmosphere, iron is preferen-
tially oxidized. In the presence of copper, this leads to sub-scale enrichment with accumulation of
high levels (5-10%) of copper and tin. A subsequently formed liquid copper-tin phase is particu-
larly harmful because of its relatively low solubility in austenite, resulting in surface hot shortness
[11].

References
1. Peters, A.T., Ferrous Production Metallurgy, John Wiley & Sons, New York, 1982.

2. Krauss, G., Principles ofHeat Treatment ofStee/, ASM International, Materials Park, Ohio,
1980.

3. Bain, E.C. and Paxton, H.W., Alloying Elements in Steel, Second Edition, ASM Interna-
tional, Materials Park, Ohio, 1966.

4. The Making, Shaping and Treating ofSteel, lOth Edition, Eds. Lankford, W.T. et al., Associ-
ation oflron and Steel Engineers, Pittsburgh, PA, 1985.

5. Higgins, R.A., Engineering Metallurgy, Part 1, Applied Physical Metallurgy, Robert E.

Krieger Publishing Company, Melbourne, Fla., 1983.

6. Andrews, K.W., "Empirical Formulae for the Calculation of Some Transformation Tempera-
tures," Journal ofthe Iron and Steel Institute, Vol. 203, 1965, pp. 721-727.

7. Shiga, C. et al., Kawasaki Steel Technical Report, No.4, 1981, pp. 97-109.

8. Metals Handbook, Eighth Edition, Vol. 1, Properties and Selection of Metals, ASM
International, Materials Park, Ohio, 1961.

9. ASM Metals Reference Book, ASM International, Materials Park, Ohio, 1981.

10. Bozorth, R.M., Ferromagnetism, D. Van Nostrand Company, Inc., Toronto, 1951.

11. Gladman, T., The Physical Metallurgy of Microalloyed Steels, The Institute ofMaterials,
London, England, 1997, pp. 38,39.