7

An Introduction to Steel

7.10 The military or industrial power of a nation has long been associated
with its ability to produce steel. The might of sixteenth-century Spain was
not unconnected with the quality of Toledo steel blades whilst in Britain
at about that time the introduction of laws limiting the felling of trees for
charcoal production, testified to the quantity of steel then being manufac-
tured. Later, the growth of the Industrial Revolution in Britain gave her
world supremacy in steel production as a result of the development of iron
and steel making by Dud Dudley and Abraham Darby and, subsequently,
by Huntsman, Bessemer, Gilchrist and Thomas. Towards the end of the
great Victorian era Britain was manufacturing most of the world's steel
and ruling an Empire on which the 'sun never set'.
During the present century depletion—and eclipse—of our home ore
supplies combined with the development of vast ore deposits overseas has
completely altered the situation. The USA and the CIS (formerly the
USSR) owe their material power largely to the presence of high-grade iron
ore within, or near to, their own considerable territories putting them
among the world leaders in steel production. Britain currently occupies
eleventh position behind the CIS, Japan, the USA, PR China, Germany,
Italy, Republic of Korea, Brazil, the Benelux Group and France having
fallen from the third position she held in the 'steel league' at the end of
the Second World War. Many other countries too are increasing their
steel-making capacities, generally from ore deposits within their own terri-
tories, so that outputs are approaching that of Britain. Of the big steel
producers West Germany and Japan, as well as Britain, have to import a
large proportion of their ore requirements.
7.11 The highest quality iron ores are the oxides magnetite, Fe3C>4, and
heamatite, FezCb, some deposits of the former containing almost 70% of
the metal. British home-produced ore is low-grade material of the carbon-
ate or hydroxide type, high in phosphorus and containing as little as 20%
iron. Fortunately it occurs near to the surface as 'sedimentary' deposits
which can be mined by open-cast methods. For this reason three-quarters
of the ore used in British blast furnaces has to be imported in the form of
high-grade concentrates from Swedish Lapland, Africa, Canada or Vene-
zuela. The principal ore producing countries are (in order of production):
CIS, PR China (and DPR Korea), Brazil, Australia, the USA, India,
Canada, South Africa, Sweden, Venezuela, Liberia, Mauretania and
France.

Pig Iron Production

7.20 The smelting of iron ore takes place in the blast furnace (Fig. 7.1).
This is a shaft-type furnace some 60 m or more in height and having an
output capacity of up to 10 000 tonnes per day. The refractory lining of
such a furnace is designed to last for several years since once the furnace
goes 'on blast' it would not be economical to shut down for re-lining.
Production takes place on a 365 days-a-year basis, though 'damping down'
—with the blast turned off or reduced—has to be used for interruptions
such as strikes.
Ore, coke and limestone are charged to the furnace through the double
bell-and-cone gas-trap system, whilst a pre-heated air blast is blown in
through tuyeres near the base of the furnace. In order to reduce coke
consumption still further and also increase furnace output fuel oil is some-

hopper
'gas gas
uptake' 'down comer

double
bdl 4 cone
throat
2OOPC

stock
line'

stack
faOO°C

I3OO°C blast
bosh main
[IBOO5Ci
tuyere
tap
hole slag hole
hearth

Fig. 7.1 The iron blast furnace. The complete structure may be sixty or more metres in
height.
times injected with the air blast. At regular intervals of several hours both
tap hole and slag hole are opened in order to run off, first the slag and
then the molten pig iron. The holes are then re-plugged with clay.
7.21 The smelting operation involves the following main chemical
reactions:
(i) Coke in the region of the tuyeres burns completely—
C + O2 -• CO2 + Heat (Exothermic)
Just above the tuyeres the carbon dioxide is reduced by the white-hot
coke to carbon monoxide—
CO2 + C - * 2CO - Heat (Exothermic)
On balance the overall reaction is strongly exothermic, so that the tempera-
ture remains high.
(ii) As the carbon monoxide, which is a powerful reducing agent, rises
through the charge it reduces the iron(III) oxide (in the ore)—
Fe 2 O 3 + 3CO-.2Fe+ 3CO2

(The reduction occurs in three stages: Fe2O3—»Fe3O4-^FeO-^Fe.) This

reaction takes place in the upper part of the furnace where the temperature
is too low for the iron so formed to melt. It therefore remains as a spongy
mass until it moves down into the lower part of the furnace where it
melts and runs down over the white-hot coke dissolving carbon, sulphur,
manganese, phosphorus and silicon as it goes. Apart from carbon—which
is absorbed from the coke—these elements are dissolved following their
reduction from compounds present as impurities in the original ore.
(iii) At the same time as this reduction is taking place, the earthy waste
or 'gangue' associated with the ore combines with lime (formed by the
decomposition of limestone added with the charge) to produce a fluid slag:

CaCO3 -• CaO + CO2

Limestone Lime

2CaO + SiO 2 -• 2CaO-SiO2

Calcium silicate (slag)

The function of the lime here is to liquefy the gangue. The latter, being
composed largely of silica, would not melt at the blast-furnace temperature
and must therefore be attacked chemically to form a low melting-point
slag which will run from the furnace.
7.22 The furnace is tapped at regular intervals, the iron generally being
stored in the molten state in a 'mixer' prior to transfer to the steel-making
plant. Some may be cast as 'pigs' for subsequent re-melting.
In the early days of this century an average blast furnace produced about
100 tonnes of pig iron per day but modern furnaces with outputs of 10 000
tonnes per day are in operation both here and abroad. The approximate
quantities of materials in both charge and products for the daily
'throughput' of a medium sized blast furnace would be:

Charge (tonnes) Products (tonnes)

Ore (say 50% iron) 4 000 Pig iron 2 000
Coke 1 800 Slag 1 600
Limestone 800 Blast furnace gas 10 800
Air 8 000 Dust 200
Total 14 600 Total 14 600

The slag produced is of low value and is used mainly for 'filling' purposes
—railway ballast, road making, concrete aggregate and for the manufac-
ture of slag wool (for thermal and accoustic insulation). It should not be
confused with the 'basic slag' used in agriculture which is a by-product of
steel-making processes.
One item in the above table which may surprise the reader is the enor-
mous volume of both air and resultant blast-furnace gas involved in the
production of a tonne of pig iron. An upwards flow of gas on this scale
demands a very porous charge in the furnace to allow the passage of gas.
For this reason the bulk of the ore used and particularly powdery imported
'concentrates', have to be 'agglomerated' before being charged to the
furnace. This involves sintering the fine material to produce strong large
lumps. Any fine ore or dust is blown out at the top of the furnace by the
upwards rush of gas. The coke too must be strong enough so that it does
not crush under the enormous pressure of the charge. Hence special cok-
ing-coal is used in its production.
7.23 The blast-furnace gas contains considerable amounts of carbon
monoxide which remain unused during reduction of the ore. Since the gas
has a useful calorific value the blast furnace performs a secondary role as
a giant gas producer and all of this gas is utilised as fuel. After being
cleaned of dust much of it is burned in the Cowper stoves which, in turn,
pre-heat the in-going air blast. Two such regenerator stoves are required
for each blast furnace. One is being re-heated by the burning blast-furnace
gas whilst the other is pre-heating the in-going air. The surplus gas is
utilised in many ways in an integrated steel-making plant, eg for raising
electric power or for firing different types of re-heating furnace used
around the plant.
7.24 Pig iron is a complex alloy. In addition to iron it contains up to
10% of other elements, the chief of which are carbon, silicon, manganese,
sulphur and phosphorus. These elements are absorbed as the reduced iron
melts and runs down through the white-hot coke and slag. The total
amount of carbon is usually 3-4% and it may be present either as iron
carbide, Fe3C (also called cementite) or as un-combined carbon {graphite).
A high silicon content of 2.5% or more favours the formation of graphite
during solidification so that a fractured surface of the solid iron is grey and
the iron is called a 'grey iron'. A low silicon content on the other hand,
say 0.5%, will favour the formation of iron carbide, Fe3C, during solidifi-
cation and the resultant iron will be a 'white iron' since the fractured
surface will show white iron carbide. However, the rate of solidification of
the iron also affects the formation of either graphite or iron carbide as it
does in cast iron (15.30). Some grades of pig iron—generally those low in
sulphur and phosphorus—are used for the manufacture of iron castings
but the bulk of pig iron produced is transferred, still molten, to the steel-
making plant.
7.25 Direct Reduction Processes The increasing scarcity of coke
suitable for use in the blast furnace has led to the development of alterna-
tive methods of iron production. Whilst the bulk of iron produced still
comes from the blast furnace, these new methods of iron production will
doubtless become much more important during the next two decades.
In some of these processes 'pelletised' high-grade ore is fed continuously
into a slowly rotating kiln which is fired by natural gas or other hydro-
carbons. The fuel provides the necessary heat and also carbon monoxide
which effects chemical reduction of the ore:
Fe2O3 + 3CO -> 2Fe + 3CO2

In a similar process the ore is contained in enclosed retorts through

which a mixture of carbon monoxide and hydrogen—derived from natural
gas—circulates. Having reduced the ore in the first retort, the 'diluted' gas
is then burned to heat the second retort, and so on. Moving-grate furnaces
are also used to carry the ore through a reducing flame provided by the
partial combustion of natural gas.
The processes mentioned briefly above employ gaseous fuels to heat and
reduce the charge, but in other methods cheap solid fuels such as coke
breeze or even lignite are used. The product of these processes is known
as 'sponge iron'. It is reasonably pure iron but unfortunately is still mixed
with the gangue present in the original ore. Since this gangue is mainly
silica it must be fluxed with lime when the sponge iron is subsequently
remelted for steel making.
7.26 Electric Iron Smelting Processes These are also used where
coke is expensive, relative to the cost of electricity, as in Scandinavia.
These processes more nearly resemble blast-furnace smelting except that
heat is supplied by an electric arc rather than by coke, though low-grade
coke is used as the reducing agent. The coke is mixed with the ore and fed
into a reaction hearth where carbon electrodes provide the heating current.
The ore is reduced by the hot coke:

Fe2O3 + 3C -* 2Fe + 3CO

Unlike the direct reduction processes mentioned above where sponge iron
is produced, the end-product here is a molten pig iron. The gas leaving
the reduction chamber is very rich in carbon monoxide so it is cleaned and
used as an energy source in the same way as blast-furnace gas.
Electric smelting of iron has the advantage that it produces less carbon
dioxide, whereas for every tonne of pig iron tapped from the blast furnace
some 3.5 tonnes of CO2 finds its way—by whatever route—into the atmos-
phere. Thus a large blast furnace producing 10 000 tonnes of pig iron per
day is responsible for discharging into the environment about 12 million
tonnes of CO2 every year. This joins the outflow of all other carbon-
burning enterprises in promoting the 'greenhouse effect'.
An alternative method of smelting iron would seem to be by using hydro-
gen as a reducing agent:

Fe2O3 + 3H2 -> 2Fe + 3H2O (which ultimately falls as tain)

The hydrogen would be provided by the electrolysis of water, using
electricity from nuclear power. This is very expensive, and the anti-nuclear
lobby would react; but do we have any long-term choice if the Earth itself
is not to 'go critical' in a rather different sense? In the short term a much
more efficient reclamation of scrap steel would help. Instead we allow
millions of tonnes to rust and 'escape' into the environment every year.

The Manufacture of Steel

7.30 Prior to the introduction of the first blast furnaces during the four-
teenth century, iron had always been reduced as a solid metal by heating
a mixture of the ore and charcoal in a hearth-type furnace. Quite small
hand-powered bellows were used to provide the air blast and the tempera-
ture attained was not high enough to melt the iron released by chemical
action from the ore. Instead particles of iron, mixed with large amounts
of slag, collected at the bottom of the hearth. These porous masses, called
blooms, were then hammered so that much of the molten slag was expelled
and a bar of relatively pure iron containing some remnant slag particles
was the result. By repeatedly forge-welding such bars together and reham-
mering into a new bar, the slag particles were elongated into fibres
(Pl. 11.1B) and wrought iron was produced. Later the reduction hearth
was replaced by a small shaft-type furnace and much larger bellows were
driven by water power. The temperature reached was sufficient to melt
the reduced iron and so the first pig iron ran from a blast furnace. This pig
iron was then remelted in an open hearth so that the impurities were
oxidised and relatively pure iron, of consequently higher melting point,
crystallised out. This was then forged to produce wrought iron as before.
Oxidation of the remelted pig iron in this way was later known as
'puddling'.
Being of quite high chemical purity wrought iron had a good resistance
to corrosion as is shown by examples of nineteenth-century shipbuilding.
Thus the hull of the four-masted sailing ship Munoz Gamer0 built in 1875
but now lying at Punta Arenasin, Chile, shows a remarkably high state of
preservation of her puddled iron plates.
7.31 By the Middle Ages wrought iron had been manufactured, by one
method or another, for some four thousand years and it is reasonable to
suppose that sooner or later some ancient craftsman would have noticed
that 'wrought iron' could be hardened by cooling it in water provided that
it had been heated in a charcoal fire for a sufficiently long time. This
ultimately led to the manufacture of steel by what was later called the
Cementation Process. Bars of wrought iron were packed into stone boxes
along with charcoal and heated at about 9000C for a week. Carbon diffused
into the solid wrought iron* and the product was forged to give a more
homogeneous steel. Such production methods were expensive and steel
was used only as a tool material. In the meantime wrought iron continued
to be used for structural and constructional work and was not finally aban-
doned until the Tay Bridge disaster of 1879 when it was probably quite
wrongly blamed for the collapse of the railway bridge.
7.32 In 1742 Benjamin Huntsman, a Sheffield clock maker, decided
that his clock springs were breaking because they lacked homogeneity, due
largely to the presence of slag in the wrought iron from which the cemen-
tation steel had been manufactured. He therefore melted bars of cemen-
tation steel so that most of the slag was lost. In this way he ultimately
perfected crucible cast steel for which Sheffield became justly famous.
7.33 Modern mass-production methods of steel manufacture began in
1856 when Henry Bessemer attempted to speed up wrought-iron manufac-
ture by blowing air through a charge of molten pig iron contained in a
pear-shaped 'converter'. Due to the high rate of the chemical reactions
involved in the oxidation of impurities such as carbon, silicon and mangan-
ese in the pig iron, the temperature ran so high that, instead of solid pure
iron crystallising out, the final product remained molten in the converter
and had to be cast. After preliminary difficulties had been overcome,
low-carbon steel suitable for constructional purposes became available for
the first time and soon the Bessemer process was established for the mass-
production of steel.
Since the Bessemer process was a very rapid production method—the
complete 'blow' lasted some half-hour—there was little time available to
control the composition and quality of the product. This led to the intro-
duction of the open-hearth process by Siemens-Martin in 1865. In this
process pig iron could be melted and refined along with large quantities of
steel scrap which was becoming available towards the end of the nineteenth
century. The main advantage however, was that the complete refining
process in the open-hearth took some eight to ten hours so that there was
ample time for control and adjustment of the composition of the product.
Until 1878 only those pig irons low in sulphur and phosphorus were
suitable for steel making since, unlike silicon, manganese and carbon, these
impurities were not oxidised and removed in the slag. Then came the
research of Thomas and Gilchrist which enabled large quantities of high-
phosphorus pig iron available in Britain to be converted to steel. To
achieve this they added lime to the furnace charge thus producing a basic
slag which would combine with phosphorus after the latter had been
oxidised:

* The process was similar in principle to modern methods of carburising for case-hardening (19.20).
 Calcium phosphate
This calcium phosphate joined the basic slag.
Thus both the Bessemer and open-hearth processes flourished in Britain
and, subsequently, elsewhere for almost a century. In either case the pro-
cess was said to be 'acid' or 'basic'. The acid processes were so called
because they utilised low-phosphorus pig irons and therefore did not
require the addition of lime to the charge. The slag formed was acid since
it contained an excess of silica (derived from oxidised silicon) and to match
this the furnace was lined with silica bricks. Those pig irons rich in phos-
phorus required the charge to be treated with lime and this produces a
basic slag. This basic slag would quickly attack ordinary acid silica brick
furnace linings and so furnaces used in basic steel making had to be lined
with a basic refractory such as 'burnt' magnesite (MgO) or 'burnt' dolomite
(MgO.CaO).
7.34 As low-phosphorus ore became scarce in Britain more and more
steel was produced by basic processes. Gradually the basic open-hearth
became the dominant steel-making process because of its capability of
producing high-quality steel from high-phosphorus raw materials. Never-
theless vast quantities of mild steel continued to be made by the Bessemer
process; though one of its chief disadvantages was that since only the
impurities present in the initial pig iron were available as fuel, to keep the
charge molten during the 'blow' no scrap could be added and the pig iron
composition had to be between close limits.
Of the air blown into the Bessemer converter only 20% by volume had
a useful function in oxidising the impurities. This of course was the oxygen.
The remaining 80% (mainly nitrogen) entered the converter cold and
emerged as hot gas, thus carrying heat away from the converter and reduc-
ing the thermal efficiency of the process. Moreover small amounts of nitro-
gen dissolved in the steel during the 'blow'. This increased the hardness of
the product and frustrated the demand for mild steel of increasing ductility
by the motor-car manufacturers and others.
7.35 In 1952 a new approach to these problems was made in steel plants
at Linz and Donnawitz in Austria. Here, instead of blowing air through
molten pig iron as in the Bessemer process, pure oxygen was injected into
the surface of molten pig iron via a water-cooled 'lance'. This process—
called the L-D process—was made possible by the introduction of cheap
'tonnage' oxygen and though this was the first major steel-making process
not to be developed in Britain, it is only fair to say that Bessemer had
been aware of the advantages of using oxygen rather than air in his original
process. Unfortunately in the nineteenth century oxygen was far too expen-
sive to produce on a large scale.

Basic Oxygen Steelmaking (BOS)

7.36 Following the introduction of L-D steelmaking in 1952 a spate of
modifications of the process followed. Thus both the Kaldo process
(Sweden) and the Rotor process (West Germany) were popular for a time
and it is inevitable that variations of the general oxygen method will
continue to be developed. Up to the time of publication all such modifi-
cations have had the following features in common:
(i) an oxygen blast is used to oxidise impurities in the original raw
material, these oxidised impurities being drawn off in the slag;
(ii) the processes are chemically basic so that phosphorus removal is
effective.
The BOF (basic oxygen furnace) is a pear-shaped vessel of up to 400
tonnes capacity, lined with magnesite bricks covered with a layer of dolo-
mite. Scrap is first loaded into the converter followed by the charge of
molten pig iron. Oxygen is then blown at the surface of the molten charge
through a water-cooled lance which is lowered through the mouth of the
converter (Fig. 7.2).
As soon as the oxidising reaction commences lime, fluorspar and millscale
are admitted to the converter to produce a slag on the surface which will
collect the impurities oxidised from the charge. At the end of the 'blow'
the slag is run off first and the charge of steel then transferred to a ladle
for casting as ingots.
BOS has the following major advantages over competing processes:
(i) It is rapid—the cycling time is about forty-five minutes;
(ii) Nitrogen contamination is very low so that deep-drawing quality
mild steel is produced;

solid molten w. c.
scrap pig iron
oxygen
lance

dolomite
magnesite-

slag

steel
slag
bogie

Fig. 7.2 Stages in the manufacture of steel in a BOF.

The water-cooled oxygen lance may be up to 0.5m in diameter and its tip between 1 and
3m above the surface of the charge—depending upon the composition of the latter.
 (iii) Thermal efficiency is high because heat is not carried away by
nitrogen as in the former Bessemer process. Hence the charge may
include 40%—and in some circumstances 50%—scrap;
(iv) A wide variety of both scrap and pig iron can be used.
The development of BOS has rendered the Bessemer process completely
obsolete whilst the open-hearth process is now used only in Eastern
Europe, India and a few Latin American plants.

Electric Arc Steelmaking

7.37 This is the only alternative steelmaking process which is significant
at present and its operation is complementary to BOS rather than competi-
tive. Originally electric-arc furnaces were used for the manufacture of small
amounts of high-grade tool steels and alloy steels. In a modern integrated
steel plant it is widely used to melt process scrap and other medium-grade
material which can be bought cheaply and then up-graded to produce very
high-quality steel. By this means the high cost of electrical energy is largely
offset. As electricity offers a chemically neutral method of providing heat,
the chemical conditions in the furnace can be altered at will to produce
either oxidising or reducing slags. The latter favour the removal of sulphur
from the charge, making the process one in which sulphur removal is
definite.
The furnace (Fig. 7.3) employs carbon rods which strike an arc on to
the charge. The lining is basic allowing the addition of lime and millscale
in order to produce a basic oxidising slag for the effective removal of
phosphorus from the charge as well as any remnant silicon or manganese.
Often the slag is then removed to be replaced by a basic reducing slag
composed of lime, anthracite and fluorspar. This removes sulphur from
the charge:

(joins slag)

SWINGING ELECTRODES
CX)OR

POURING CHARGING
SPOUT DOOR

ARC
SLAG

STEEL

Fig. 7.3 The principles of the electric-arc furnace for steelmaking.

 Hence the main advantages of the arc process are:
(i) Removal of sulphur is reliable;
(ii) Conditions are chemically 'clean' and contamination of the charge
is impossible;
(iii) Temperature can be accurately controlled;
(iv) Carbon content can be adjusted between fine limits;
(v) The addition of alloying elements can be made with precision.
Currently about a quarter of Britain's steel production comes from elec-
tric processes. The remainder is from BOS.

The Microstructural Nature of Carbon Steels

7.40 Despite the development of many sophisticated alloys in recent
years ordinary steel seems likely to remain the most important engineering
alloy available. Hence it has been considered desirable to make a prelimi-
nary study of the structures and properties of carbon steels at this stage in
preparation for a more detailed study later in the book.
It is impossible adequately to study the structure of a steel, or any other
alloy, without reference to what are called 'thermal equilibrium diagrams'
—or 'phase diagrams'. Probably some readers will have been introduced
to the iron-carbon thermal equilibrium diagram during preliminary studies
of materials science. The purpose of this chapter is to clarify such ideas as
those readers may have formulated on the subject and also to introduce
other readers to this important field of physical metallurgy. Both phase
diagrams in general, and that for iron and carbon in particular, will be
discussed in succeeding chapters. We will begin by studying the method of
construction and also the interpretation of a simple thermal equilibrium
diagram by reference to some tin-lead alloys.
7.41 Most readers will be aware that there are two main varieties of
tin-lead solder. Best-quality tinman's solder contains 62% tin and 38%
lead* and its solidification begins and ends at the same temperature—
183°C (Fig. 7.4(iii)). Plumber's solder, however, contains 33% tin and 67%
lead, and whilst it begins to solidify at about 265°C, solidification is not
complete until 183°C (Fig. 7.4(i)). Between 265 and 183°C, then, plumber's
solder is in a pasty, partly solid state which enables the plumber to 'wipe'
a joint with the aid of his 'cloth' (20.21).
From observations such as these it can be concluded that the temperature
range over which a tin-lead alloy solidifies depends upon its composition.
On further investigation it will be found that an alloy containing 50% tin
and 50% lead will begin to solidify at 2200C, and be completely solid at
183°C; whilst one containing 80% tin and 20% lead will begin to solidify
at 2000C and finish solidifying at 1830C.
From the data accumulated above we can draw a diagram which will
indicate the state in which any given tin-lead alloy (within the range of

* Whilst for reasons of economy tinman's solder often contains less than 62% tin (20.21), the latter
composition is ideal, since the solder will melt and freeze quickly at a fixed temperature.
 °C °C °C 0
C

TIME TIME TIME TIME

33% tin 5O°h t i n 62°/o tin 86<*>tin

Fig. 7.4 Temperature/time cooling curves for various tin/lead alloys. Points (a) indicate the
temperature at which solidification begins, and points {b) the temperature at which it ends.

compositions investigated) will exist at any given temperature (Fig. 7.5).

This diagram has been obtained by plotting the temperatures at which the
alloys mentioned above begin and finish solidifying, on a temperature-
composition diagram. All points—a\, a2, a3, a4—at which the various alloys
begin to solidify, are joined, as are the points—b\, bi, b3, b4—where
solidification is complete.
Any alloy represented in composition and temperature by a point above
AEB will be in a completely molten state, whilst any alloy similarly rep-
resented by a point below CED will be completely solid. Likewise, any
alloy whose temperature and composition are represented by a point
between AE and CE or between EB and ED will be in a part liquid-part
solid state.
7.42 Such a diagram is of great use to the metallurgist, and is called a
thermal-equilibrium diagram—or phase diagram. The meaning of the term

completely liquid
C
0

liquid
TEMPERATURE

+
solid
(pasty stage) liquid + solid

completely solid

plumber's tinman's
solder solder
IOO^btin
O^o lead
COMPOSITION Wo BY WEIGHT)

Fig. 7.5 A diagram showing the relationship between composition, temperature and physi-
cal state for the range of tin/lead alloys studied. This is part of the tin/lead thermal equilibrium
diagram.
'equilibrium' in this thermodynamical context will become apparent as a
result of later studies in this book, but for the moment we will consider an
everyday example which goes some way to illustrate its meaning.
On a hot summer's day we can produce a delightfully refreshing drink
by putting a cube of ice into a glass of lager. The contents of the glass,
however, are not in thermal equilibrium with the surroundings, and as
heat-transfer takes place into the lager the ice ultimately melts and the
liquid warms up, so that the whole becomes more homogeneous if less
palatable. Rapid cooling, as we shall see later, often produces an alloy
structure which, like the ice and lager, is not in thermal equilibrium at
room temperature. The basic difference between the ice-lager mixture and
the non-equilibrium metallic structure is that the former is able to reach
'structural' equilibrium with ease, due to the great mobility of the constitu-
ent particles, but in the case of the metallic structure rearrangement of the
atoms is more difficult, since they are retained by considerable forces of
attraction in an orderly pattern in a crystal lattice. A non-equilibrium
metallic structure produced by rapid cooling may therefore be retained
permanently at room temperature.
7.43 If we assume that a series of alloys has been cooled slowly enough
for structural equilibrium to obtain, then the thermal-equilibrium diagram
will indicate the relationship which exists between composition, tempera-
ture and microstructure of the alloys concerned. By reference to the dia-
gram, we can, for an alloy of any composition in the series, find exactly
what its structure or physical condition will be at any given temperature.
We can also in many cases forecast with a fair degree of accuracy the
effect of a particular heat-treatment on the alloy; for in modern metallurgy
heat-treatment is not a process confined to steels, but is applied also to
many non-ferrous alloys. These are two of the more important uses of the
thermal-equilibrium diagram as a metallurgical tool. Let us now proceed
with our preliminary study of the iron-carbon alloys, with particular refer-
ence to their equilibrium diagram.
7.50 Plain carbon steels are generally defined as being those alloys of
iron and carbon which contain up to 2.0% carbon. In practice most ordi-
nary steels also contain appreciable amounts of manganese residual from
a deoxidation process carried out prior to casting. For the present, how-
ever, we shall neglect the effects of this manganese and regard steels as
being simple iron-carbon alloys.
7.51 As we have seen (3.14), the pure metal iron, at temperatures
below 9100C, has a body-centred cubic structure, and if we heat it to above
this temperature the structure will change to one which is face-centred
cubic. On cooling, the change is reversed and a body-centred cubic
structure is once more formed. The importance of this reversible transfor-
mation lies in the fact that up to 2.0% carbon can dissolve in face-
centred cubic iron, forming what is known as a 'solid solution',* whilst
* We shall deal more fully with the nature of solid solutions in the next chapter, and for the present it
will be sufficient to regard a solid solution as being very much like a liquid solution in that particles of the
added metal are absorbed without visible trace, even under a high-power microscope, into the structure
of the parent metal.
in body-centred cubic iron no more than 0.02% carbon can dissolve in
this way.
7.52 As a piece of steel in its face-centred cubic form cools slowly and
changes to its body-centred cubic form, any dissolved carbon present in
excess of 0.02% will be precipitated, whilst if it is cooled rapidly enough
such precipitation is prevented. Upon this fact depends our ability to heat-
treat steels—and, in turn, the present advanced state of our twentieth-
century technology.
7.53 The solid solution formed when carbon atoms are absorbed into
the face-centred cubic structure of iron is called Austenite and the
extremely low level of solid solution formed when carbon dissolves in
body-centred cubic iron is called Ferrite. For many practical purposes we
can regard ferrite as having the same properties as pure iron. In most
text-books on metallurgy the reader will find that the symbol y ('gamma')
is used to denote both the face-centred cubic form of iron and the solid-
solution austenite, whilst the symbol a ('alpha') is used to denote both the
body-centred cubic form of iron existing below 9100C and the solid-solution
ferrite. The same nomenclature will be used in this book.
When carbon is precipitated from austenite it is not in the form of
elemental carbon (graphite), but as the compound iron carbide, FQ3C,
usually called Cementite. This substance, like most other metallic carbides,
is very hard, so that, as the amount of carbon (and hence, of cementite)
increases, the hardness of the slowly cooled steel will also increase.
7.54 Fig. 7.5 indicates the temperatures at which solidification begins
and ends for any homogeneous liquid solution of tin and lead. In the same
way Fig. 7.6 shows us the temperatures at which transformation begins and
ends for any solid solution (austenite) of carbon and face-centred cubic
iron. Just as the melting point of either tin or lead is lowered by adding each
to the other, so is the allotropic transformation temperature of face-centred
cubic iron altered by adding carbon. Fig. 7.6 includes only a part of the
whole iron-carbon equilibrium diagram, but it is the section which we
make use of in the heat-treatment of carbon steels. On the extreme left
of this diagram is an area labelled 'ferrite'. This indicates the range of
temperatures and compositions over which carbon can dissolve in body-
centred cubic (a) iron. On the left of the sloping line AB all carbon present
is dissolved in the body-centred cubic iron, forming the solid-solution fer-
rite, whilst any point representing a composition and temperature to the
right of AB indicates that the solid-solution a is saturated, so that some of
the carbon contained in the steel will be present as cementite. The signifi-
cance of the slope of AB is that the solubility of carbon in body-centred
cubic iron increases from 0.006% at room temperature to 0.02% at 723°C.
Temperature governs the degree of solubility of solids in liquids in exactly
the same way.
7.55 We will now study the transformations which take place in the
structures of three representative steels which have been heated to a tem-
perature high enough to make them austenitic and then allowed to cool
slowly. If a steel containing 0.40% carbon is heated to some temperature
above Ui it will become completely austenitic (Fig. 7.6(i)). On cooling
again to just below Ui (which is called the 'upper critical temperature' of
the steel), the structure begins to change from one which is face-centred
cubic to one which is body-centred cubic. Consequently, small crystals of
body-centred cubic iron begin to separate out from the austenite. These
body-centred cubic crystals (Fig. 7.6(ii)) retain a small amount of carbon
(less than 0.02%), so we shall refer to them as crystals of ferrite. As the
temperature continues to fall the crystals of ferrite grow in size at the
expense of the austenite (Fig. 7.6(iii)), and since ferrite is almost pure
iron, it follows that most of the carbon present accumulates in the shrinking
crystals of austenite. Thus, by the time our piece of steel has reached Li
(which is called its 'lower critical temperature') it is composed of approxi-
mately half ferrite (containing only 0.02% carbon) and half austenite,
which now contains 0.8% carbon. The composition of the austenite at this
stage is represented by E. Austenite can hold no more than 0.8% carbon
in solid solution at this temperature (723°C), therefore, as the temperature
falls still farther, the carbon begins to precipitate as cementite. At the
same time ferrite is still separating out and we find that these two sub-
stances, ferrite and cementite, form as alternate layers until all the remain-
ing austenite is used up (Fig. 7.6(iv)). This laminated structure of ferrite
and cementite, then, will contain exactly 0.8% carbon, so that it will
account for approximately half the volume of our 0.4% carbon steel. It is
an example of what, in metallurgy, we call a eutectoid (8.43). This particu-
lar eutectoid is known as Pearlite because when present on the etched
surface of steel it acts as a 'diffraction grating', splitting up white light into
its component spectrum colours and giving the surface a 'mother of pearl'
sheen. In order to be able to see these alternate layers of ferrite and
cementite of which pearlite is composed, a metallurgical microscope cap-
able of a magnification in the region of 500 diameters is necessary.
Any steel containing less than 0.8% carbon will transform from austenite
to a mixture of ferrite and pearlite in a similar way when cooled from its
austenitic state. Transformation will begin at the appropriate upper critical
temperature (given by a point on CE which corresponds with the compo-
sition of the steel) and end at the lower critical temperature of 723°C. The
relative amounts of ferrite and pearlite will depend upon the carbon con-
tent of the steel (Fig 7.7), but in every case the ferrite will be almost pure
iron and the pearlite will contain exactly 0.8% carbon.
7.56 A steel containing 0.8% carbon will not begin to transform from
austenite on cooling until the point E is reached. Then transformation will
begin and end at the same temperature (723°C), just as tinman's solder
solidifies at a single temperature (183°C). Since the steel under consider-
ation contained 0.8% carbon initially, it follows that the final structure will
be entirely pearlite (Fig 7.6(vi)).
7.57 A steel which contains, say, 1.2% carbon will begin to transform
from austenite when the temperature falls to its upper critical at Ui. Since
the carbon is this time in excess of the eutectoid composition, it will begin
to precipitate first; not as pure carbon but as needle-shaped crystals of
cementite round the austenite grain boundaries (Fig 7.6(viii)). This will
cause the austenite to become progressively less rich in carbon, and by the
 AUSTENITE
FERRITE
CEMENTITE

AUSTENITE

FERRITE + AUSTENITE CEMENTITE + AUSTENITE

FERRITE
FERRITE + ! CEMENTITE

(FERRITE + PEARLITE) (CEMENTITE + PEARLITE)

CARBON °/o

Fig. 7.6 Part of the iron-carbon thermal equilibrium diagram.

time a temperature of 723°C has been reached the remaining austenite will
contain only 0.8% carbon. This remaining austenite will then transform to
pearlite (Fig 7.6(x)), as in the two cases already dealt with.
Any steel containing more than 0.8% carbon will have a structure con-
sisting of cementite and pearlite if it is allowed to cool slowly from its
austenitic state. Since the pearlite part of the structure always contains
alternate layers of ferrite and cementite in the correct proportions to give
an overall carbon content of 0.8% for the pearlite, it follows that any
variation in the total carbon content of the steel above 0.8% will cause a
corresponding variation in the amount of primary cementite present. (The
terms 'primary cementite' and 'primary ferrite' are used to denote that
cementite or ferrite which forms first, before the residual austenite trans-
forms to pearlite.)
A plain carbon steel which contains less than 0.8% carbon is generally
referred to as a hypo-eutectoid steel, whilst one containing more than
0.8% carbon is known as a hyper-eutectoid steel. Naturally enough, a plain
carbon steel containing exactly 0.8% carbon is called a eutectoid steel.
7.60 So far we have been dealing only with the types of structure
produced when plain carbon steels are cooled slowly from the austenitic
condition. Such conditions prevail during industrial processes such as
normalising and annealing. By very rapid cooling from the austenitic con-
dition, such as would be obtained by water-quenching, another structure,
called Martensite, is formed. This does not appear on the equilibrium
diagram simply because it is not an equilibrium structure. Rapid cooling
has prevented equilibrium from being reached.
7.61 As most readers will already know, martensite is very hard indeed.
Unfortunately it is also rather brittle, and the steel is used in this condition
only when extreme hardness is required. To increase the steel's toughness
after quenching (at the expense of a fall in hardness) the steel can be
tempered. A modification in the structure will take place depending upon
the tempering temperature. This temperature will vary between 250 and
6500C according to the combination of mechanical properties required in
the finished component. Whatever temperature is used, tempering assists
the microstructure to proceed in some measure back towards equilibrium,
with the precipitation of microscopical particles of cementite in varying
amounts from the original martensitic structure. The type of structure
formed by tempering at about 4000C was formerly known as Troostite,
whilst that produced in the region of 6000C used to be called Sorbite.
Metallurgists now discourage the use of these terms for reasons which will
be explained later when the heat-treatment of steel is discussed more fully
in Chapters 11 and 12.

The Uses of Plain Carbon Steels

7.70 By varying the amount of carbon in a steel, and by selecting a
heat-treatment programme suited to that carbon content, we are able to
produce a vast range of different mechanical properties such as are avail-
able in no other metallic alloy. Moreover, carbon steel is a relatively inex-
pensive alloy when compared with non-ferrous alloys generally. Small
wonder then that steel is by far our most important engineering alloy.
Possibly its most serious fault is that it rusts and we must often spend
considerable amounts of money on protecting its surface from atmospheric
corrosion (21.10).
TENSILE STRENGTH (N/mm 2 )
HARDNESS Hb

ELONGATION PER CENT

CEMENTlTE
°/o

FERRITE
PEARLlTE

PEARLITE

CARBON PER CENT

screws screw drills saws

drivers taps
tinplatc razors
r.s.j. rails dies
structural wire
steels ropes
chains axles shear blades knives
stampings gears cold chisels broaches
rivets shafts some hand tools reamers
wire tyres
nails
Fig. 7.7 A diagram showing the relationship between carbon content, microstructure and
mechanical properties of plain carbon steels in the normalised condition. Typical uses of
these steels are also indicated.
 As shown in Fig. 7.7, the hardness of a plain carbon steel increases
progressively with increase in carbon content, so that generally the low-
and medium-carbon steels are used for structural and constructional work,
whilst the high-carbon steels are used for the manufacture of tools and
other components where hardness and wear-resistance are necessary.
Commercial plain carbon steels may be classified into five groups as
indicated in Table 7.1 which, along with Fig. 7.7, indicates some of the
common uses of these alloys.

Table 7.1

Percentage Uses
Type of steel carbon

0.05-0.15 Chain, stampings, rivets, wire, nails, seam-welded pipes,

Dead mild mattresses, hot- and cold-rolled strip for many purposes

0.10-0.20 Structural steels, RSJ, screws, machine parts, tin-plate,

Mild case-hardening, drop-forgings, stampings
0.20-0.30 Machine and structural work, gears, free-cutting steels, shafting,
levers, forgings

0.30-0.40 Connecting-rods, shafting, wire, axles, fish-plates, crane hooks,

Medium carbon high-tensile tubes, forgings
0.40-0.50 Crankshafts, axles, gears, shafts, die-blocks, rotors, tyres,
heat-treated machine parts
0.50-0.60 Loco tyres, rails, laminated springs, wire ropes

0.60-0.70 Drop-hammer dies, set-screws, screw-drivers, saws, mandrels,

High carbon caulking tools, hollow drills
0.70-0.80 Band saws, anvil faces, hammers, wrenches, laminated springs,
car bumpers, small forgings, cable wire, dies, large dies for cold
presses
0.80-0.90 Cold chisels, shear blades, cold setts, punches, rock drills, some
hand tools

Tool steels 0.90-1.00 Springs, high-tensile wire, axes, knives, dies, picks
1.00-1.10 Drills, taps, milling cutters, knives, screwing dies
1.10-1.20 Ball bearings, dies, drills, lathe tools, woodworking tools
1.20-1.30 Files, reamers, knives, broaches, lathe and wood-working tools
1.30-1.40 Saws, razors, boring and finishing tools, machine parts where
resistance to wear is essential

Exercises
1. Show how the exploitation of new iron ore fields has helped to change the
balance of world power during the present century. (7.10)
2. What advantages has 'direct reduction' over the blast-furnace process for pig
iron production? (7.25)
3. Outline the essential chemistry common to all modern steel-making processes.
(7.33-7.36)
4. Discuss both the economic and technical advantages of modern BOS processes
as compared with the obsolete Bessemer process. (7.36)
5. Why has electric-arc steelmaking survived despite the high cost of electric
power? (7.37)
6. Relate the changes in microstructure to the properties of normalised steels as
the carbon content increases from 0.1 to 1.2%. Comment on the choice of
carbon content for some typical engineering applications. (7.50)
7. Show how the mechanical properties of tensile strength, % elongation and
hardness for normalised plain-carbon steels vary with carbon content up to
1.2%.
Sketch and label the microstructures of the following normalised steels
(i) 0.2%C; (ii) 0.8%C; (iii) 1.2%C. (Fig 7.7)

Bibliography
Peters, A. J., Ferrous Production Metallurgy, John Wiley, 1982.
United States Steel Corporation, The Making, Shaping and Treatment of Steel.
BS 970: 1973 and 1988 Wrought Steels in the Form of Blooms, Billets, Bars and
Forgings (Part 1—carbon steels).
BS 4659: 1971 Tool Steels.