Ferrous Alloys

: The Science and Engineering of Materials, 4th ed

by Donald R.
R Askeland Pradeep P
P. Phul

Designations and Classification of Steels

Simple Heat Treatments
Isothermal Heat Treatments
Quench and Temper
Q
p Heat Treatments
Effect of Alloying Elements
Application of Hardenability
Specialty Steels
Surface Treatments
Weldability of Steel
Stainless Steels
C
Cast
IIrons

General Categories
g
of Ferrous
Metals and Alloys
Carbon and alloy steels
Stainless steel
Tool and Die steel
Cast Irons
Cast Steels
**Ferrous tools first appear
pp
about 4000 to 3000 BC,
made from meteoritic iron. Real ironworking started
in about 1100 BC in Asia Minor, and started the Iron
Age.
g

Production of Iron and Steel

Raw Materials for Production

Iron Ore

Limestone ----------

Coke

Raw Materials

Pig Iron

The three raw materials are dumped into a blast

furnace.
Hot air (2000*F) is blasted into the furnace, which
helps drive the chemical reaction.
reaction The coke forms CO
and the CO reduces the iron oxide to iron.
The slag floats to the top and the metal is transferred
to molds and cools. IT IS NOW PIG IRON, ready for
more iron work or steelmaking.
steelmaking

Blast
Furnace

Tuyeres
Iron Ore + Coke + Limestone + Air
(1.93)
(0.96)
(0.48)
(3.93)
Pig Iron + Slag + Gases + Flue Dust
(1.0)
(0.55)
(5.68)
(0.09)

(Same height as a 10 story building)

(a)In a blast furnace, iron ore is

reduced using coke (carbon) and
air to produce liquid pig iron. The
high-carbon content in the pig iron
is reduce by
y introducing
g oxygen
yg
into the basic oxygen furnace to
produce liquid steel. An electric
arc furnace can be used to
produce liquid steel by melting
scrap.
(b) Schematic of a blast furnace
operation. (Source:
www.steel.org. Used with
permission of the American Iron
and Steel Institute.)

Pig Iron

Steel

To make steel you are simply removing more

impurities, such as, manganese, silicon, carbon,
from the pig iron.
iron
Impurities are removed by re
re-melting
melting the metal and
adding carbon, steel scrap, and more limestone.
The metal can be melted using one of three methods.
Open-Hearth furnace
Electric furnace
Basic Oxygen furnace. (BOF)

Open-Hearth Furnace

Uses a fuel to generate heat, and melt the metal.

Basic-Oxygen Furnace

Fastest steelmaking process can

make 250 tons of steel / hour
Melted pig iron and scrap are poured
(charged) into a vessel.
Fluxing agents are added, like
limestone.
The molten metal is blasted with pure
oxygen. This produces iron oxide which
then reacts with carbon to produce CO
and CO2.
CO2 The slag floats to the top of
the metal.
Higher steel quality than open hearth.
Used to make plate, sheet, I-beam,
t bing and
tubing
nd channel.
h nnel

Electric Furnace

Uses electric arc from electrode to metal to heat and melt it.
Can produce 60
60-90
90 tons of steel per day.
Steel is higher quality than open-hearth and BOF

Vacuum Furnace
Uses induction furnaces.
Air is removed from the furnace, this removes the
gaseous impurities from the molten metal.
Produces very high-quality steel.

Killed Semi-Killed Rimmed Steel

Killed Steel This is a fully deoxidized steel, and thus,
has no porosity.
This
hi is
i accomplished
li h d b
by using
i
elements
l
lik
like
aluminum to de-oxidize the metal. The impurities
rise and mix with the slag.
g
It is called killed because when the metal is poured
it has no bubbles, it is quiet.
Because it is so solid, not porous, the ingot shrinks
considerably when it cools, and a pipe or
g cavity
y forms. This must be cut off and
shrinkage
scrapped.

Killed Semi-Killed Rimmed Steel

Semi-Killed Steel: This is practically the same as killed steel,
with
h some minor differences.
d ff
It is only partially de-oxidized, and therefore, is a little
more porous than killed steel.
Semi-Killed does not shrink as much as it cools, so the pipe
is much smaller and scrap is reduced.
It is much more economical and efficient to produce.
p
Rimmed Steel: This is produced by adding elements like
aluminum to the molten metal to remove unwanted gases
gases.
The gasses then form blowholes around the rim.
Results in little or no piping.
HOWEVER, impurities also tend to collect in the center of
the ingot, so products or rimmed steel need to be
inspected and tested.

Continuous Casting
-Molten metal skips
ingot step
step, and goes
directly the furnace to
a tundish
-Metal solidifies in the mold
-The metal descends @ about 1/sec
-The solidified metal then goes through
pinch rollers that determine the final
form.

B
Benefits
fit off Continuous
C ti
Casting
C ti
Costs less to produce final product
Metal has more uniform composition and properties
than ingot processing.

(a)In a blast furnace, iron ore is

reduced using coke (carbon) and
air to produce liquid pig iron. The
high-carbon content in the pig iron
is reduce by
y introducing
g oxygen
yg
into the basic oxygen furnace to
produce liquid steel. An electric
arc furnace can be used to
produce liquid steel by melting
scrap.
(b) Schematic of a blast furnace
operation. (Source:
www.steel.org. Used with
permission of the American Iron
and Steel Institute.)

Designations and Classification

of Steels
Designations - The AISI (American Iron and Steel
Institute) and SAE (Society of Automotive Engineers)
provide designation systems for steels that use a four- or
five-digit number.
Cl
Classifications
ifi
i
- Steels
S
l can be
b classified
l
ifi d based
b
d on their
h i
composition or the way they have been processed.

2003 Brooks/Cole, a divisiion of Thomson Learning, Innc. Thomson Learning is a trademark used herein underr license.

(a)The eutectoid
portion of the Fe
FeFe3C phase
diagram.
(b) An expanded
version of the Fe-C
diagram, adapted
from several
sources.

Electron micrographs of (a) pearlite,

pearlite (b) bainite,
bainite and (c)
tempered martensite, illustrating the differences in cementite
size and shape among these three microconstituents (
7500). (From The Making, Shaping, and Treating of Steel,
10th Ed. Courtesy of the Association of Iron and Steel
Engineers.)

Simple Heat Treatments

Process Annealing
g Eliminating
g Cold Work: A lowtemperature heat treatment used to eliminate all or part
of the effect of cold working in steels.
Annealing and Normalizing Dispersion Strengthening:
Annealing - A heat treatment used to produce a soft,
coarse pearlite in steel by austenitizing, then furnace
cooling.
li
N
Normalizing
li i
- A simple
i
l h
heatt ttreatment
t
t obtained
bt i d
by austenitizing and air cooling to produce a fine pearlitic
structure.
Spheroidizing Improving Machinability: Spheroidite - A
microconstituent containing coarse spheroidal cementite
particles in a matrix of ferrite, permitting excellent
machining characteristics in high-carbon steels.

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Schematic summary of the simple heat treatments for

(a) hypoeutectoid steels and (b) hypereutectoid steels.
steels

2003 Brooks/Cole, a diivision of Thomson Learningg, Inc. Thomson Learning is a trademark used herein unnder license.

The effect of carbon and

heat treatment on the
properties of plain
plain-carbon
carbon
steels.

The microstructure of spheroidite, with

Fe3C particles dispersed in a ferrite matrix
( 850). (From ASM Handbook, Vol. 7,
(1972), ASM International, Materials Park,
OH 44073.)
44073 )

Isothermal Heat Treatments

Austempering - The isothermal heat treatment by which
austenite transforms to bainite.
Isothermal annealing - Heat treatment of a steel by
austenitizing, cooling rapidly to a temperature between
the A1 and the nose of the TTT curve,, and holding
g until
the austenite transforms to pearlite.

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

The austempering
Th
t
i
and
d isothermal
i th
l anneall heat
h t treatments
t
t
t in
i a
1080 steel.

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learningg is a trademark used hereinn under license.

The TTT diagrams for (a) a

1050 and ((b)) a 10110 steel.

22003 Brooks/Cole, a divisionn of Thomson Learning, Inc. Thomson Learning is a traademark used herein under liicense.

Producing
P
d i
complicated
li
d
structures by interrupting
the isothermal heat
t
treatment
t
t off a 1050
steel.

Dark feathers of bainite surrounded

by light martensite, obtained by
interrupting the isothermal
transformation process ( 1500).
(ASM Handbook, Vol. 9 Metallography
and Microstructure (1985) )

Quench and Temper Heat Treatments

Retained austenite - Austenite that is unable to
transform into martensite during quenching because of
the volume expansion associated with the reaction.
reaction
Tempered martensite - The microconstituent of ferrite
and cementite formed when martensite is tempered.
Quench cracks - Cracks that form at the surface of a
steel during quenching due to tensile residual stresses
that are produced because of the volume change that
accompanies the austenite-to-martensite transformation.
Marquenching - Quenching austenite to a temperature
just above the MS and holding until the temperature is
equalized throughout the steel before further cooling to
produce martensite.

The effect of tempering

p
g
temperature on the
mechanical properties of
a 1050 steel.

Retained austenite (white) trapped

between martensite needles (black)
( 1000). (From ASM Handbook, Vol.
8, (1973))

Increasing carbon
reduces the Ms and Mf
temperatures in plaincarbon steels.

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Formation
o at o of
o quench
que c cracks
c ac s caused by residual
es dua stresses
st esses produced
p oduced during
du g
quenching. The figure illustrates the development of stresses as the
austenite transforms to martensite during cooling.

The marquenching heat

treatment designed to
reduce residual stresses
ands quench cracking.
cracking

The CCT diagram (solid lines) for a 1080 steel compared with the
TTT diagram (dashed lines).

The CCT diagram for a low-alloy, 0.2% C Steel.

Effect of Alloying Elements

Hardenability - Alloy steels have high hardenability.
Effect on the Phase Stability - When alloying elements
are added to steel,
steel the binary Fe-Fe
Fe Fe3C stability is
affected and the phase diagram is altered.
Shape of the TTT Diagram - Ausforming is a
thermomechanical heat treatment in which austenite is
plastically deformed below the A1 temperature, then
permitted to transform to bainite or martensite.
Tempering - Alloying elements reduce the rate of
tempering compared with that of a plain-carbon steel.

(a)TTT Curve
(b) CCT curves for a 4340 steel.

The effect of 6%
manganese on the
stability ranges of the
phases
h
in
i the
h eutectoid
id
portion of the Fe-Fe3C
phase diagram.

When alloying elements introduce a bay region into the TTT

diagram, the steel can be ausformed.

The effect of alloying elements on the phases formed during the

tempering of steels. The air-hardenable steel shows a secondary
hardening peak.

Application of Hardenability
Jominy test - The test used to evaluate hardenability. An
austenitized steel bar is quenched at one end only, thus
producing a range of cooling rates along the bar.
bar
Hardenability curves - Graphs showing the effect of the
cooling rate on the hardness of as-quenched steel.
Jominy distance - The distance from the quenched end of
a Jominy bar. The Jominy distance is related to the
cooling rate.

The set-up for the Jominy test used for determining the
hardenability of a steel.

The hardenability
curves for several
steels.

The Grossman chart used to determine the hardenability at the

center of a steel bar for different quenchants.

The hardenability curves

for several steels.

Specialty Steels
Tool steels - A group of high-carbon steels that provide
combinations of high hardness, toughness, or resistance
to elevated temperatures.
temperatures
Secondary hardening peak - Unusually high hardness in
a steel tempered at a high temperature caused by the
precipitation off alloy
ll
carbides.
bd
Dual-phase steels - Special steels treated to produce
martensite dispersed in a ferrite matrix.
Maraging steels - A special class of alloy steels that
obtain high strengths by a combination of the
martensitic and age-hardening
age hardening reactions.
reactions

Microstructure of a dual-phase steel,

steel
showing islands of light martensite in a
ferrite matrix ( 2500). (From G.
Speich, Physical Metallurgy of DualPhase Steels, Fundamentals of DualPhase Steels, The Metallurgical Society
of AIME, 1981.)

Surface Treatments
Selectively Heating the Surface - Rapidly heat the
surface of a medium-carbon steel above the A3
temperature and then quench the steel.
Case depth - The depth below the surface of a steel at
which hardening occurs by surface hardening and
carburizing
gp
processes.
Carburizing - A group of surface-hardening techniques
by which carbon diffuses into steel.
C
Cyaniding
idi
- Hardening
H d i
th
the surface
f
off steel
t l with
ith carbon
b
and nitrogen obtained from a bath of liquid cyanide
solution.
Carbonitriding - Hardening the surface of steel with
carbon and nitrogen obtained from a special gas
atmosphere.

(a) Surface hardening by localized heating. (b) Only the surface

heats above the A1 temperature and is quenched to martensite.

Carburizing of a low-carbon steel to produce a high-carbon, wearresistant surface.

Weldability of Steel
The d
Th
development
l
t off the
th
heat-affected zone in a
weld:
(a) the structure at the
maximum temperature,
(b) the structure after
cooling in a steel of low
h d
hardenability,
bilit and
d (c)
( ) the
th
structure after cooling in
a steel of high
hardenability.
y

Stainless Steels
Stainless steels - A group of ferrous alloys that contain
at least 11% Cr, providing extraordinary corrosion
resistance.
resistance
Categories of stainless steels:
Ferritic Stainless Steels
Martensitic Stainless Steels
Austenitic Stainless Steels
Precipitation-Hardening
P
i i i
H d i
(PH) S
Stainless
i l
S
Steels
l
Duplex Stainless Steels

(a) The effect of 17%

chromium on the iron-carbon
phase diagram. At low-carbon
contents, ferrite is stable at all
temperatures. (b) A section of
the iron-chromium-nickelcarbon phase diagram at a
constant 18% Cr-8% Ni.
Ni At
low-carbon contents, austenite
is stable at room
temperatures.

(a) Martensitic stainless steel containing large primary carbides and small
carbides formed during tempering ( 350).
350) (b) Austenitic stainless steel (
500). (From ASM Handbook, Vols. 7 and 8, (1972, 1973))

Cast Irons
Cast iron - Ferrous alloys containing sufficient carbon so
that the eutectic reaction occurs during solidification.
Eutectic and Eutectoid reaction in Cast Irons
Types of cast irons:
Gray cast iron
White cast iron
Malleable cast iron
Ductile or nodular, cast iron
Compacted graphite cast iron

Schematic drawings of the five types of cast iron: (a) gray iron, (b) white
iron, (c) malleable iron, (d) ductile iron, and (e) compacted graphite iron.

The iron-carbon
iron carbon phase diagram showing the relationship between the stable
iron-graphite equilibria (solid lines) and the metastable iron-cementite
reactions (dashed lines).

The transformation diagram for austenite in a cast iron.

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((a)) Sk
Sketch
t h and
d (b) photomicrograph
h t
i
h off the
th flake
fl k graphite
hit in
i
gray cast iron (x 100).

The effect of the

cooling rate or casting
size on the tensile
properties of two gray
cast irons.

The heat treatments for ferritic and pearlitic malleable irons.

(a) White cast iron prior to heat treatment ( 100). (b) Ferritic malleable iron with
graphite nodules and small MnS inclusions in a ferrite matrix ( 200).
200) (c) Pearlitic
malleable iron drawn to produce a tempered martensite matrix ( 500). (Images (b)
and (c) are from Metals Handbook, Vols. 7 and 8, (1972, 1973)) (d) Annealed ductile
iron with a ferrite matrix ( 250). (e) As-cast ductile iron with a matrix of ferrite
(white) and pearlite ( 250). (f) Normalized ductile iron with a pearlite matrix ( 250).

The CCT diagram for a low-alloy, 0.2% C steel.

The hardenability
curves for several
steels.

(b) A section of the ironchromium nickel carbon

chromium-nickel-carbon
phase diagram at a constant
18% Cr-8% Ni. At lowcarbon contents, austenite
i stable
is
bl at room
temperature.

Classification of Ferrous Alloys

Metal Alloys

Ferrous

Nonferrous

Cast Irons

Steels

Gray Ductile White Malleable

iron iron
iron
i
iron

Low Alloy

High Alloy
Low-carbon
Low
carbon Medium
Medium-carbon
carbon High
High-carbon
carbon

High
Plain strength,
low alloy

Plain

Heat
treatable Plain Tool

Stainless

Classification of Ferrous Alloys

Based on carbon content
Pure iron (< 0.008wt% C)
From the phase diagram,
it is composed almost
exclusively of the ferrite
phase at room
temperature.
Steels (0.008 ~ 2.14wt% C)
I mostt steels
In
t l the
th microstructure
i
t
t
consists
i t off both
b th and
d Fe
F 3C
phases.
Carbon concentrations in commercial steels rarely exceed 1.0
wt%.
Cast irons (2.14 ~ 6.70wt% C)
Commercial cast irons normally contain less than 4.5wt% C

Ferrous Alloys Steels

The carbon content is normally less than 1.0 wt%.
Plain carbon steels: containing only residual
concentrations of impurities other than carbon and a little
manganese
About 90% of all steel made is carbon steel.
Alloy steels: more alloying elements are intentionally
added in specific concentrations.
Stainless steels

Classification of Steels
A
According
di to
t Their
Th i Carbon
C b Contents
C t t
Low-carbon steels

L
Less
than
th 0.25
0 25 wt%C
t%C
Medium-carbon steels

0.25 ~ 0.60 wt%C

High-carbon steels

0.60 ~ 1.4 wt%C

The Designation of Steels

A four-digit number:

th first
the
fi t two
t
digits
di it indicate
i di t the
th alloy
ll content;
t t
the last two, the carbon concentration
For plain carbon steels, the first two digits are 1 and 0;
alloy steels are designated by other initial two-digit
combinations (e.g., 13, 41, 43)
The third and fourth digits represent the weight percent
carbon multiplied by 100
For example, a 1040 steel is a plain carbon steel
containing 0.40 wt% C.

The Designation of Steels

A four-digit number: the first two digits indicate the alloy
content;; the last two,, the carbon concentration

41 40
Identifies
major alloying
element(s)
( )

Percentage
P
t
of carbon

Table 11.2a AISI/SAE and UNS Designation Systems

AISI: American Iron and Steel Institute

SAE: Society of Automotive Engineers
UNS: Uniform Numbering System

Steel Alloys
S t e e l N u me r ic a l Na me
10XX, 11 XX
13XX
23XX 25 XX
23XX,
31XX, 33XX, 303XX
40XX
41XX
43XX & 47XX
44XX
48XX
50XX, 51XX, 501XX, 521XX,
61XX
81XX, 86XX, 87XX, 88XX
92XX
93XX, 98XX
94XX
XXBXX
XXLXX
94XX Ni-

Key Alloys
Carbon only
Manganese
Ni k l
Nickel
Nickel-Chromium
Mo
Cr-Mo
Ni-Cr-Mo
Mn-Mo
Ni-Mo
Cr
Cr-V
Ni-Cr-Mo
Si-Mn
Ni-Cr-Mo
Ni-Cr-Mo-Mn
Boron
Lead

Low-Carbon Steels
Less than 0
0.25
25 wt%C
Unresponsive to heat treatments intended to form martensite;
strengthening is accomplished by cold work
Microstructures: ferrite and pearlite
Relatively
y soft and weak,, but having
g outstanding
g ductility
y
and toughness
Typically, y = 275 MPa, UT = 415~550 MPa, and ductility =
2 %E
25%EL
Machinable, weldable, and, of all steels, are the least
expensive to produce
Applications: automobile body components, structural
shapes,
p
and sheets used in pipelines,
pp
buildings,
g bridges,
g
etc.

TTT Diagram of Some Hypoeutectoid Alloys

Table 11.1a
Compositions of Five Plain Low-Carbon Steels

Table 11.1b
Mechanical Characteristics of Hot-Rolled Material and
Typical Applications for Various Plain Low-Carbon Steels

Medium-Carbon Steels
0.25 ~ 0.60 wt%C
May be heat treated by austenitizing, quenching, and then
tempering to improve their mechanical properties
Stronger than low-carbon steels and weaker than high-carbon
steels
T i l Tensile
Typical
T
il Properties
P
ti for
f Oil-Quenched
Oil Q
h d and
d Tempered
T
d Plain
Pl i Carbon
C b

a Classified as high-carbon steels

High-Carbon Steels
0.60 ~ 1.4 wt%C
Used in a hardened and tempered condition
Hardest, strongest, and yet least ductile; especially wear
resistant and capable
p
of holding
g a sharp
p cutting
g edge
g
Containing Cr, V, W, and Mo; these alloying elements
combine with carbon to form very hard and wear-resistant
carbide compounds (e.g., Cr23C6, V4C3, and WC)
Applications: cutting tools and dies for forming and
shaping
h i
materials,
t i l knives,
k i
razors, hacksaw
h k
blades,
bl d
springs,
i
and high-strength wire

Table 11.3 Designations,

g
, Compositions,
p
,
and Applications for Six Tool Steels

Comparison of the Advantages

Off
Offered
db
by C
Carbon
b St
Steels
l and
d All
Alloy St
Steels
l
Carbon Steel

Alloy Steel

Lower cost

Higher strength

Greater availability
y

Better wear
Toughness
Special high temperature
behavior
Better corrosion
resistance
Special electrical
properties

94XX Ni-

Alloy steel is more expensive than carbon steel; it should

be used only when a special property is needed.

Table 11.2a AISI/SAE and UNS Designation

g
Systems
y

Stainless Steels
Stainless steels are selected for their excellent resistance to
corrosion.
Stainless steels are divided into three classes: martensitic,
ferritic, or austenitic
The predominant alloying element is chromium; a
concentration of at least 11 wt% Cr is required

It permits a thin, protective surface layer of chromium

oxide to form when the steel is exposed to oxygen.
The chromium is what makes stainless steel
stainless!