The Effects of Alloying Elements on Iron-Carbon

Alloys
Abstract: The simplest version of analyzes the effects of alloying elements on iron-carbon alloys would
require analysis of a large number of ternary alloy diagrams over a wide temperature range. However,
Wever pointed out that iron binary equilibrium systems fall into four main categories: open and closed field systems, and expanded and contracted -field systems.
The form of the diagram depends to some degree on the electronic structure of the alloying elements
which is reflected in their relative positions in the periodic classification.
The simplest version of analyzes the effects of alloying elements on iron-carbon alloys would require
analysis of a large number of ternary alloy diagrams over a wide temperature range. However, Wever
pointed out that iron binary equilibrium systems fall into four main categories (Fig. 1): open and closed field systems, and expanded and contracted -field systems. This approach indicates that alloying
elements can influence the equilibrium diagram in two ways:
by expanding the -field, and encouraging the formation of austenite over wider compositional
limits. These elements are called -stabilizers.
by contracting the -field, and encouraging the formation of ferrite over wider compositional
limits. These elements are called -stabilizers.
The form of the diagram depends to some degree on the electronic structure of the alloying elements
which is reflected in their relative positions in the periodic classification.

Figure 1. Classification of iron alloy phase diagrams: a. open -field; b. expanded -field; c. closed field
(Wever, Archiv, Eisenhttenwesen, 1928-9, 2, 193)
Class 1: open -field. To this group belong the important steel alloying elements nickel and manganese,
as well as cobalt and the inert metals ruthenium, rhodium, palladium, osmium, iridium and platinum.
Both nickel and manganese, if added in sufficiently high concentration, completely eliminate the bcc iron phase and replace it, down to room temperature, with the -phase. So nickel and manganese depress
the phase transformation from to to lower temperatures (Fig. 1a), i.e. both Ac 1 and Ac3 are lowered. It
is also easier to obtain metastable austenite by quenching from the -region to room temperature,
consequently nickel and manganese are useful elements in the formulation of austenitic steels.
Class 2: expanded -field. Carbon and nitrogen are the most important elements in this group. The phase field is expanded, but its range of existence is cut short by compound formation (Fig.1b). Copper,
zinc and gold have a similar influence. The expansion of the -field by carbon, and nitrogen, underlies the
whole of the heat treatment of steels, by allowing formation of a homogeneous solid solution (austenite)
containing up to 2.0 wt % of carbon or 2.8 wt % of nitrogen.

Class 3: closed -field. Many elements restrict the formation of -iron, causing the -area of the diagram
to contract to a small area referred to as the gamma loop (Fig. 1c). This means that the relevant elements
are encouraging the formation of bcc iron (ferrite), and one result is that the - and -phase fields become
continuous. Alloys in which this has taken place are, therefore, not amenable to the normal heat
treatments involving cooling through the /-phase transformation. Silicon, aluminium, beryllium and
phosphorus fall into this category, together with the strong carbide forming elements, titanium, vanadium,
molybdenum and chromium.
Class 4: contracted y-field. Boron is the most significant element of this group, together with the carbide
forming elements tantalum, niobium and zirconium. The -loop is strongly contracted, but is
accompanied by compound formation (Fig. 1d).
The distribution of alloying elements in steels. Although only binary systems have been considered so
far, when carbon is included to make ternary systems the same general principles usually apply. For a
fixed carbon content, as the alloying clement is added the y-field is either expanded or contracted
depending on the particular solute.
With an element such as silicon the -field is restricted and there is a corresponding enlargement of the field. If vanadium is added, the -field is contracted and there will be vanadium carbide in equilibrium
with ferrite over much of the ferrite field. Nickel does not form a carbide and expands the -field.
Normally elements with opposing tendencies will cancel each other out at the appropriate combinations,
but in some cases anomalies occur. For example, chromium added to nickel in a steel in concentrations
around 18% helps to stabilize the -phase, as shown by 18Cr8Ni austenitic steels.
One convenient way of illustrating quantitatively the effect of an alloying element on the -phase field of
the Fe-C system is to project on to the Fe-C plane of the ternary system the -phase field boundaries for
increasing concentration of a particular alloying element. For more precise and extensive information, it
is necessary to consider series of isothermal sections in true ternary systems Fe-C-X, but even in some of
the more familiar systems the full information is not available, partly because the acquisition of accurate
data can be a difficult and very time-consuming process.
Recently the introduction of computer-based methods has permitted the synthesis of extensive
thermochemical and phase equilibria data, and its presentation in the form, for example, of isothermal
sections over a wide range of temperatures.
If only steels in which the austenite transforms to ferrite and carbide on slow cooling are considered, the
alloying elements can be divided into three categories:

elements which enter only the ferrite phase

elements which form stable carbides and also enter the ferrite phase
elements which enter only the carbide phase.

In the first category there are elements such as nickel, copper, phosphorus and silicon which, in
transformable steels, are normally found in solid solution in the ferrite phase, their solubility in cementite
or in alloy carbides being quite low.
The majority of alloying elements used in steels fall into the second category, in so far as they are carbide
formers and as such, at low concentrations, go into solid solution in cementite, but will also form solid
solutions in ferrite. At higher concentrations most will form alloy carbides, which are thermodynamically
more stable than cementite.
Typical examples are manganese, chromium, molybdenum, vanadium, titanium, tungsten and niobium.
Manganese carbide is not found in steels, but instead manganese enters readily into solid solution in Fe 3C.
The carbide-forming elements are usually present greatly in excess of the amounts needed in the carbide
phase, which are determined primarily by the carbon content of the steel. The remainder enters into solid
solution in the ferrite with the non-carbide forming elements nickel and silicon. Some of these elements,
notably titanium, tungsten, and molybdenum, produce substantial solid solution hardening of ferrite.

In the third category there are a few elements which enter predominantly the carbide phase. Nitrogen is
the most important element and it forms carbo-nitrides with iron and many alloying elements. However,
in the presence of certain very strong nitride forming elements, e.g. titanium and aluminum, separate alloy
nitride phases can occur.
While ternary phase diagrams, Fe-C-X, can be particularly helpful in understanding the phases which can
exist in simple steels, isothermal sections for a number of temperatures are needed before an adequate
picture of the equilibrium phases can be built up. For more complex steels the task is formidable and
equilibrium diagrams can only give a rough guide to the structures likely to be encountered. It is,
however, possible to construct pseudobinary diagrams for groups of steels, which give an overall view of
the equilibrium phases likely to be encountered at a particular temperature.
Structural changes resulting from alloying additions. The addition to iron-carbon alloys of elements
such as nickel, silicon, manganese, which do not form carbides in competition with cementite, does not
basically alter the microstructures formed after transformation. However, in the case of strong carbideforming elements such as molybdenum, chromium and tungsten, cementite will be replaced by the
appropriate alloy carbides, often at relatively low alloying element concentrations. Still stronger carbide
forming elements such as niobium, titanium and vanadium are capable of forming alloy carbides,
preferentially at alloying concentrations less than 0.1 wt%.
It would, therefore, be expected that the microstructures of steels containing these elements would be
radically altered. It has been shown how the difference in solubility of carbon in austenite and ferrite leads
to the familiar ferrite/cementite aggregates in plain carbon steels. This means that, because the solubility
of cementite in austenite is much greater than in ferrite, it is possible to redistribute the cementite by
holding the steel in the austenite region to take it into solution, and then allowing transformation to take
place to ferrite and cementite. Examining the possible alloy carbides, and nitrides, in the same way, shows
that all the familiar ones are much less soluble in austenite than is cementite.
Chromium and molybdenum carbides are not included, but they are substantially more soluble in
austenite than the other carbides. Detailed consideration of such data, together with practical knowledge
of alloy steel behavior, indicates that, for niobium and titanium, concentrations of greater than about 0.25
wt % will form excess alloy carbides which cannot be dissolved in austenite at the highest solution
temperatures. With vanadium the limit is higher at 1-2%, and with molybdenum up to about 5%.
Chromium has a much higher limit before complete solution of chromium carbide in austenite becomes
difficult. This argument assumes that sufficient carbon is present in the steel to combine with the alloying
element. If not, the excess metallic element will go into solid solution both in the austenite and the ferrite.
In general, the fibrous morphology represents a closer approach to an equilibrium structure so it is more
predominant in steels which have transformed slowly. In contrast, the interphase precipitation and
dislocation nucleated structures occur more readily in rapidly transforming steels, where there is a high
driving force, for example, in microalloyed steels.
The clearest analogy with pearlite is found when the alloy carbide in lath morphology forms nodules in
association with ferrite. These pearlitic nodules are often encountered at temperatures just below Ac 1, in
steels which transform relatively slowly.
For example, these structures are obtained in chromium steels with between 4% and 12% chromium and
the crystallography is analogous to that of cementitic pearlite. It is, however, different in detail because of
the different crystal structures of the possible carbides. The structures observed are relatively coarse, but
finer than pearlite formed under equivalent conditions, because of the need for the partition of the
alloying element, e.g. chromium between the carbide and the ferrite. To achieve this, the interlamellar
spacing must be substantially finer than in the equivalent iron-carbon case.
Interphase precipitation. Interphase precipitation has been shown to nucleate periodically at the /
interface during the transformation. The precipitate particles form in bands which are closely parallel to
the interface, and which follow the general direction of the interface even when it changes direction
sharply. A further characteristic is the frequent development of only one of the possible Widmansttten

variants, for example VC plates in a particular region are all only of one variant of the habit, i.e. that in
which the plates are most nearly parallel to the interface.
The extremely fine scale of this phenomenon in vanadium steels, which also occurs in Ti and Nb steels, is
due to the rapid rate at which the / transformation takes place. At the higher transformation
temperatures, the slower rate of reaction leads to coarser structures. Similarly, if the reaction is slowed
down by addition of further alloying elements, e.g. Ni and Mn, the precipitate dispersion coarsens.
The scale of the dispersion also varies from steel to steel, being coarsest in chromium, tungsten and
molybdenum steels where the reaction is relatively slow, and much finer in steels in which vanadium,
niobium and titanium are the dominant alloying elements and the transformation is rapid.
Transformation diagrams for alloy steels. The transformation of austenite below the eutectoid
temperature can best be presented in an isothermal transformation diagram, in which the beginning and
end of transformation is plotted as a function of temperature and time. Such curves are known as timetemperature-transformation, or TTT curves, and form one of the important sources of quantitative
information for the heat treatment of steels.
In the simple case of a eutectoid plain carbon steel, the curve is roughly C-shaped with the pearlite
reaction occurring down to the nose of the curve and a little beyond. At lower temperatures bainite and
martensite are formed. The diagrams become more complex for hypo- and hyper-eutectoid alloys as the
ferrite or cementite reactions have also to be represented by additional lines.

The Iron-Carbon Equilibrium Diagram

Abstract: A study of the constitution and structure of all steels and irons must first start with the ironcarbon equilibrium diagram. Many of the basic features of this system influence the behavior of even the
most complex alloy steels.
For example, the phases found in the simple binary Fe-C system persist in complex steels, but it is
necessary to examine the effects alloying elements have on the formation and properties of these phases.
The iron-carbon diagram provides a valuable foundation on which to build knowledge of both plain
carbon and alloy steels in their immense variety.
A study of the constitution and structure of all steels and irons must first start with the iron-carbon
equilibrium diagram. Many of the basic features of this system (Fig. 1) influence the behavior of even the
most complex alloy steels. For example, the phases found in the simple binary Fe-C system persist in
complex steels, but it is necessary to examine the effects alloying elements have on the formation and
properties of these phases. The iron-carbon diagram provides a valuable foundation on which to build
knowledge of both plain carbon and alloy steels in their immense variety.

Fig. 1. The iron-carbon diagram.

It should first be pointed out that the normal equilibrium diagram really represents the metastable
equilibrium between iron and iron carbide (cementite). Cementite is metastable, and the true equilibrium
should be between iron and graphite. Although graphite occurs extensively in cast irons (2-4 wt % C), it is
usually difficult to obtain this equilibrium phase in steels (0.03-1.5 wt %C). Therefore, the metastable
equilibrium between iron and iron carbide should be considered, because it is relevant to the behavior of
most steels in practice.
The much larger phase field of -iron (austenite) compared with that of -iron (ferrite) reflects the much
greater solubility of carbon in -iron, with a maximum value of just over 2 wt % at 1147C (E, Fig.1).
This high solubility of carbon in -iron is of extreme importance in heat treatment, when solution
treatment in the -region followed by rapid quenching to room temperature allows a supersaturated solid
solution of carbon in iron to be formed.
The -iron phase field is severely restricted, with a maximum carbon solubility of 0.02 wt% at 723C (P),
so over the carbon range encountered in steels from 0.05 to 1.5 wt%, -iron is normally associated with
iron carbide in one form or another. Similarly, the -phase field is very restricted between 1390 and
1534C and disappears completely when the carbon content reaches 0.5 wt% (B).
There are several temperatures or critical points in the diagram, which are important, both from the basic
and from the practical point of view.

Firstly, there is the A1, temperature at which the eutectoid reaction occurs (P-S-K), which is 723C
in the binary diagram.
Secondly, there is the A3, temperature when -iron transforms to -iron. For pure iron this occurs
at 910C, but the transformation temperature is progressively lowered along the line GS by the
addition of carbon.
The third point is A4 at which -iron transforms to -iron, 1390C in pure iron, hut this is raised as
carbon is added. The A2, point is the Curie point when iron changes from the ferro- to the
paramagnetic condition. This temperature is 769C for pure iron, but no change in crystal
structure is involved. The A1, A3 and A4 points are easily detected by thermal analysis or
dilatometry during cooling or heating cycles, and some hysteresis is observed. Consequently, three
values for each point can be obtained. Ac for heating, Ar for cooling and Ae (equilibrium}, but it
should be emphasized that the Ac and Ar values will be sensitive to the rates of heating and
cooling, as well as to the presence of alloying elements.

The great difference in carbon solubility between - and -iron leads normally to the rejection of carbon
as iron carbide at the boundaries of the phase field. The transformation of to - iron occurs via a
eutectoid reaction, which plays a dominant role in heat treatment.
The eutectoid temperature is 723C while the eutectoid composition is 0.80% C(s). On cooling alloys
containing less than 0,80% C slowly, hypo-eutectoid ferrite is formed from austenite in the range 910723C with enrichment of the residual austenite in carbon, until at 723C the remaining austenite, now
containing 0.8% carbon transforms to pearlite, a lamellar mixture of ferrite and iron carbide (cementite).
In austenite with 0,80 to 2,06% carbon, on cooling slowly in the temperature interval 1147C to 723C,
cementite first forms progressively depleting the austenite in carbon, until at 723C, the austenite contains
0.8% carbon and transforms to pearlite.
Steels with less than about 0.8% carbon are thus hypo-eutectoid alloys with ferrite and pearlite as the
prime constituents, the relative volume fractions being determined by the lever rule which states that as
the carbon content is increased, the volume percentage of pearlite increases, until it is 100% at the
eutectoid composition. Above 0.8% C, cementite becomes the hyper-eutectoid phase, and a similar
variation in volume fraction of cementite and pearlite occurs on this side of the eutectoid composition.
The three phases, ferrite, cementite and pearlite are thus the principle constituents of the infrastructure of
plain carbon steels, provided they have been subjected to relatively slow cooling rates to avoid the
formation of metastable phases.

The austenite- ferrite transformation

Under equilibrium conditions, pro-eutectoid ferrite will form in iron-carbon alloys containing up to 0.8 %
carbon. The reaction occurs at 910C in pure iron, but takes place between 910C and 723C in ironcarbon alloys.
However, by quenching from the austenitic state to temperatures below the eutectoid temperature Ae 1,
ferrite can be formed down to temperatures as low as 600C. There are pronounced morphological
changes as the transformation temperature is lowered, which it should be emphasized apply in general to
hypo-and hyper-eutectoid phases, although in each case there will be variations due to the precise
crystallography of the phases involved. For example, the same principles apply to the formation of
cementite from austenite, but it is not difficult to distinguish ferrite from cementite morphologically.

The austenite-cementite transformation

The Dube classification applies equally well to the various morphologies of cementite formed at
progressively lower transformation temperatures. The initial development of grain boundary
allotriomorphs is very similar to that of ferrite, and the growth of side plates or Widmanstaten cementite
follows the same pattern. The cementite plates are more rigorously crystallographic in form, despite the
fact that the orientation relationship with austenite is a more complex one.

As in the case of ferrite, most of the side plates originate from grain boundary allotriomorphs, but in the
cementite reaction more side plates nucleate at twin boundaries in austenite.

The austenite-pearlite reaction

Pearlite is probably the most familiar micro structural feature in the whole science of metallography. It
was discovered by Sorby over 100 years ago, who correctly assumed it to be a lamellar mixture of iron
and iron carbide.
Pearlite is a very common constituent of a wide variety of steels, where it provides a substantial
contribution to strength. Lamellar eutectoid structures of this type are widespread in metallurgy, and
frequently pearlite is used as a generic term to describe them.
These structures have much in common with the cellular precipitation reactions. Both types of reaction
occur by nucleation and growth, and are, therefore, diffusion controlled. Pearlite nuclei occur on austenite
grain boundaries, but it is clear that they can also be associated with both pro-eutectoid ferrite and
cementite. In commercial steels, pearlite nodules can nucleate on inclusions.

Iron and Its Interstitial Solid Solutions

Abstract: Steels form perhaps the most complex group of alloys in common use. Therefore, in studying
them it is useful to consider the behavior of pure iron first, then iron-carbon alloys, and finally examine
the many complexities which arise when further alloying additions are made.
Pure iron is not an easy material to produce. However, it has recently been made with a total impurity
content not exceeding 60 ppm (parts per million). Iron of this purity is extremely weak: the resolved shear
stress of a single crystal at room temperature can be as low as 10 MPa, while the yield stress of a
polycrystalline sample at the same temperature can be well below 150 MPa.
The study of steels is important because steels represent by far the most widely used metallic materials,
primarily due to the fact that they can be manufactured relatively cheaply in large quantities to very
precise specifications. They also provide an extensive range of mechanical properties from moderate
strength levels (200-300MPa) with excellent ductility and toughness, to very high strengths (2000 MPa)
with adequate ductility. It is, therefore, not surprising that irons and steels comprise well over 80% by
weight of the alloys in general industrial use.
Steels form perhaps the most complex group of alloys in common use. Therefore, in studying them it is
useful to consider the behavior of pure iron first, then iron-carbon alloys, and finally examine the many
complexities which arise when further alloying additions are made.
Pure iron is not an easy material to produce. However, it has recently been made with a total impurity
content not exceeding 60 ppm (parts per million), of which 10 ppm is accounted for by non-metallic
impurities such as carbon, oxygen, sulphur, phosphorus, while 50 ppm represents the metallic impurities.
Iron of this purity is extremely weak: the resolved shear stress of a single crystal at room temperature can
be as low as 10 MPa, while the yield stress of a polycrystalline sample at the same temperature can be
well below 150 MPa.

The phase transformation: - and - iron

Pure iron exists in two crystal forms, one body-centred cubic (bcc) (-iron, ferrite) which remains stable
from low temperatures up to 910C (the A3 point), when it transforms to a face-centred cubic (fcc) form
(-iron, austenite). The -iron on remains stable until 1390C, the A4 point, when it reverts to bcc form,
(now -iron) which remains stable up to the melting point of 1536C.
The detailed geometry of unit cells of - and -iron crystals is particularly relevant to, for example, the
solubility in the two phases of non-metallic elements such as carbon and nitrogen, the diffusivity of
alloying elements at elevated temperatures, and the general behavior on plastic deformation.

The bcc structure of -iron is more loosely packed than that of fcc -iron. The largest cavities in the bcc
structure are the tetrahedral holes existing between two edge and two central atoms in the structure, which
together form a tetrahedron.
It is interesting that the fcc structure, although more closely-packed, has larger holes than the bccstructure. These holes are at the centers of the cube edges, and are surrounded by six atoms in the form of
an octagon, so they are referred to as octahedral holes.
The transformation in pure iron occurs very rapidly, so it is impossible to retain the hightemperature fcc form at room temperature. Rapid quenching can substantially alter the morphology of the
resulting -iron, but it still retains its bcc structure.

Carbon and nitrogen in solution in - and - iron

The addition of carbon to iron is sufficient to form a steel. However, steel is a generic term which covers
a very large range of complex compositions. The presence of even a small concentration of carbon, e.g.
0.1-0.2 weight per cent (wt%); approximately 0.5-1.0 atomic per cent, has a great strengthening effect on
iron, a fact known to smiths over 2500 years ago since iron heated in a charcoal fire can readily absorb
carbon by solid state diffusion. However, the detailed processes by which the absorption of carbon into
iron converts a relatively soft metal into a very strong and often tough alloy have only recently been fully
explored.
The atomic sizes of carbon and nitrogen are sufficiently small relative to that of iron to allow these
elements to enter the - iron and &gamma- iron lattices as interstitial solute atoms. In contrast, the
metallic alloying elements such as manganese, nickel and chromium have much larger atoms, i.e. nearer
in size to those of iron, and consequently they enter into substitutional solid solution.
However, comparison of the atomic sizes of C and N with the sizes of the available interstices makes it
clear that some lattice distortion must take place when these atoms enter the iron lattice. Indeed, it is
found that C and N in -iron occupy not the larger tetrahedral holes, but the octahedral interstices which
are more favorably placed for the relief of strain, which occurs by movement of two nearest neighbor iron
atoms. In the case of tetrahedral interstices, four iron atoms are of nearest-neighbor status and the
displacement of these would require more strain energy. Consequently these interstices are not preferred
sites for carbon and nitrogen atoms.
The solubility of both C and N in austenite should be greater than in ferrite, because of the larger
interstices available. It is, therefore, reasonable to expect that during simple heat treatments, excess
carbon and nitrogen will be precipitated. This could happen in heat treatments involving quenching from
the state, or even after treatments entirely within the field, where the solubility of C varies by nearly
three orders of magnitude between 720C and 20C.
Precipitation of carbon and nitrogen from -iron. -iron containing about 0.02 wt % C is substantially
supersaturated with carbon if, after being held at 700C, it is quenched to room temperature. This
supersaturated solid solution is not stable, even at room temperature, because of the ease with which
carbon can diffuse in -iron. Consequently, in the range 20-300C, carbon is precipitated as iron carbide.
This process has been followed by measurement of changes in physical properties such as electrical
resistivity, internal friction, and by direct observation or the structural changes in the electron microscope.
The process of ageing is a two-stage one. The first stage takes place at temperatures up to 200C and
involves the formation or a transitional iron carbide phase () with a close-packed hexagonal structure
which is often difficult to identify, although its morphology and crystallography have been established. It
forms as platelets on {100} planes, apparently homogenously in the -iron matrix, but at higher ageing
temperatures (150-200C) nucleation occurs preferentially on dislocations. The composition is between
Fe2.4C and Fe3C.
Ageing at 200C and above leads to the second stage of ageing in which orthorhombic cementite Fe 3C is
formed as platelets on {110}. Often the platelets grow on several {110} planes from a common centre
giving rise to structures which appear dendritic in character. The transition from -iron carbide to

cementite is difficult to study, but it appears to occur by nucleation of cementite at the -carbide/
interlaces, followed by re-solution of the metastable -carbide precipitate.
The maximum solubility of nitrogen in ferrite is 0.10 wt %, so a greater volume fraction of nitride
precipitate can be obtained. The process is again two-stage with a be tetragonal " phase, Fe 16N2, as the
intermediate precipitate, forming as discs on {100}, matrix planes both homogeneously and on
dislocations. Above about 200C, this transitional nitride is replaced by the ordered fcc , Fe4N.
The ageing of -iron quenched from a high temperature in the -range is usually referred to as quench
ageing, and there is substantial evidence to show that the process can cause considerable strengthening,
even in relatively pure iron. In commercial low carbon steels, nitrogen is usually combined with
aluminium, or present in too low concentration to make a substantial contribution to quench ageing, with
the result that the major effect is due to carbon. This behavior should be compared with that of strain
ageing.
Some practical aspects. The very rapid diffusivity of carbon and nitrogen in iron compared with that of
the metallic alloying elements is exploited in the processes of carburizing and nitriding.
Carburizing can be carried out by heating a low carbon steel in contact with carbon to the austenitic
range, e.g. 1000C, where the carbon solubility, c 1, is substantial. The result is a carbon gradient in the
steel, from c1 at the surface in contact with the carbon, to c at a depth.
The diffusion coefficient D of carbon in iron actually varies with carbon content, so the above
relationship is not rigorously obeyed. Carburizing, whether carried out using carbon, or more efficiently
using a carburizing gas (gas carburizing), provides a high carbon surface on a steel, which, after
appropriate heat treatment, is strong and wear resistant.
Nitriding is normally carried out in an atmosphere of ammonia, but at a lower temperature (500-550C)
than carburizing, consequently the reaction occurs in the ferrite phase, in which nitrogen has a
substantially higher solubility than carbon.
Nitriding steels usually contain chromium (1%), aluminum (1%), vanadium or molybdenum (0.2%),
which are nitride-forming elements, and which contribute to the very great hardness of the surface layer
produced.

Designation of Carbon and Low-Alloy Steels

Abstract: A designation is the specific identification of each grade, type, or class of steel by a number,
letter, symbol, name, or suitable combination. Unique to a particular steel grade, type and class are terms
used to classify steel products. Within the steel industry, they have very specific uses: grade is used to
denote chemical composition; type is used to indicate deoxidation practice; and class is used to describe
some other attribute, such as strength level or surface smoothness. This article describes basics of SAE,
AISI, UNS, AMS, European and Japanese designation systems.
A designation is the specific identification of each grade, type, or class of steel by a number, letter,
symbol, name, or suitable combination. Unique to a particular steel grade, type and class are terms used to
classify steel products. Within the steel industry, they have very specific uses: grade is used to denote
chemical composition; type is used to indicate deoxidation practice; and class is used to describe some
other attribute, such as strength level or surface smoothness.
In ASTM specifications, however, these terms are used somewhat interchangeably. In ASTM A 533, for
example, type denotes chemical composition, while class indicates strength level. In ASTM A 515, grade
identifies strength level; the maximum carbon content permitted by this specification depends on both
plate thickness and strength level. In ASTM A 302 grade denotes requirements for both chemical
composition and mechanical properties. ASTM A 514 and A 5117 are specifications for high-strength
quenched and tempered plate for structural and pressure vessel applications, respectively, each contains

several compositions that can provide the required mechanical properties. However, A 514 type A has the
identical composition limits as A 517 grade.
Chemical composition is by far the most widely used basis for classification and/or designation of steels.
The most commonly used system of designation in the United States is that of the Society of Automotive
Engineers (SAE) and the American Iron and Steel Institute (AISI). The Unified Numbering System
(UNS) is also being used with increasing frequency.

SAE-AISI Designations
As stated above, the most widely used system for designating carbon and alloy steels is the SAE-AISI
system. As a point of technicality, there are two separate systems, but they are nearly identical and have
been carefully coordinated by the two groups. It should be noted, however, that AISI has discontinued the
practice of designating steels.
The SAE-AISI system is applied to semi-finished forgings, hot-rolled and cold-finished bars, wire rod
and seamless tubular goods, structural shapes, plates, sheet, strip, and welded tubing.
Carbon steels contain less than 1.65% Mn, 0.60% Si, and 0.60% Cu; they comprise the lxxx groups in
the SAE-AISI system and are subdivided into four distinct series as a result of the difference in certain
fundamental properties among them.
Designations for merchant quality steels include the prefix M. A carbon steel designation with the letter B
inserted between the second and third digits indicates the steel contains 0.0005 to 0.003% B. Likewise,
the letter L inserted between the second and third digits indicates that the steel contains 0.15 to 0.35% Pb
for enhanced machinability. Resulfurized carbon steels of the 11xx group and resulfurized and
rephosphorized carbon steels of the 12xx group are produced for applications requiring good
machinability. Steels that having nominal manganese contents of between 0.9 and 1.5% but no other
alloying additions now have 15xx designations in place of the 10xx designations formerly used.
Alloy steels contain manganese, silicon, or copper in quantities greater than those listed for the carbon
steels, or they have specified ranges or minimums for one or more of the other alloying elements. In the
AISI-SAE system of designations, the major alloying elements are indicated by the first two digits of the
designation. The amount of carbon, in hundredths of a percent, is indicated by the last two (or three)
digits.
For alloy steels that have specific hardenability requirements, the suffix H is used to distinguish these
steels from corresponding grades that have no hardenability requirement. As with carbon steels, the letter
B inserted between the second and third digits indicates that the steel contains boron. The prefix E
signifies that the steel was produced by the electric furnace process.
HSLA Steels. Several grades of HSLA steel are described in SAE Recommended Practice J410. These
steels have been developed as a compromise between the convenient fabrication characteristics and low
cost of plain carbon steels and the high strength of heat-treated alloy steels. These steels have excellent
strength and ductility as-rolled.
UNS Designations The Unified Numbering System (UNS) has been developed by ASTM and SAE and
several other technical societies, trade associations, and United States government agencies.
A UNS number, which is a designation of chemical composition and not a specification, is assigned to
each chemical composition of a metallic alloy. The UNS designation of an alloy consists of a letter and
five numerals. The letters indicate the broad class of alloys; the numerals define specific alloys within that
class. Existing designation system, such as the AISI-SAE system for steels, have been incorporated into
UNS designations. UNS is described in greater detail in SAE J1086 and ASTM E 527.

AMS Designation
Aerospace Materials Specifications (AMS), published by SAE, are complete specifications that are
generally adequate for procurement purposes. Most of the AMS designations pertain to materials intended
for aerospace applications; the specifications may include mechanical property requirements significantly
more severe than those for grades of steel having similar compositions but intended for other applications.
Processing requirements, such as for consumable electrode remelting, are common in AMS steels.
ASTM (ASME) Specifications The most widely used standard specifications for steel products in the
United States are those published by ASTM. These are complete specifications, generally adequate for
procurement purposes. Many ASTM specifications apply to specific products, such as A 574 for alloy
steel socket head cap screws. These specifications are generally oriented toward performance of the
fabricated end product, with considerable latitude in chemical composition of the steel used to make the
end product.
ASTM specifications represent a consensus among producers, specifiers, fabricators, and users of steel
mill products. In many cases, the dimensions, tolerances, limits, and restrictions in the ASTM
specifications are similar to or the same as the corresponding items of the standard practices in the AISI
Steel Products Manuals.
Many of the ASTM specifications have been adopted by the American Society of Mechanical Engineers
(ASME) with little or no modification; ASME uses the prefix S and the ASTM designation for these
specifications. For example, ASME-SA213 and ASTM A 213 are identical.
Steel products can be identified by the number of the ASTM specification to which they are made. The
number consists of the letter A (for ferrous materials) and an arbitrary, serially assigned number. Citing
the specification number, however, is not always adequate to completely describe a steel product. For
example, A 434 is the specification for heat-treated (hardened and tempered) alloy steel bars. To
completely describe steel bars indicated by this specification, the grade (SAE-AISI designation in this
case) and class (required strength level) must also be indicated. The ASTM specification A 434 also
incorporates, by reference, two standards for test methods (A 370 for mechanical testing and E 112 for
grain size determination) and A 29, which specifies the general requirements for bar products.
SAE-AISI designations for the compositions of carbon and alloy steels are sometimes incorporated into
the ASTM specifications for bars, wires, and billets for forging. Some ASTM specifications for sheet
products include SAE-AISI designations for composition. The ASTM specifications for plates and
structural shapes generally specify the limits and ranges of chemical composition directly, without the
SAE.AISI designations.
General Specifications. Several ASTM specifications, such as A 20 covering steel plate used for pressure
vessels, contain the general requirements common to each member of a broad family of steel products.
These general specifications are often supplemented by additional specifications describing a different
mill form or intermediate fabricated product.

European and Japanese Designation Systems

Below some basics of European and Japanese designation systems are explained. Please refer to articles
about corresponding national and international standards for more details.
DIN standards are developed by Deutsches Institut fur Normung in the Federal Republic of Germany.
All West German steel specifications are preceded by the uppercase letters DIN followed an alphanumeric
or numeric code. The latter method, known as the Werkstoff number, uses numbers only with a decimal
point after the first digit.
JIS standards are developed by the Japanese Industrial Standards Committee, which is part of the
Ministry of International Trade and Industry in Tokyo. The JIS steel specifications begin with the
uppercase letters JIS and are followed by an uppercase letter (G in the case of carbon and low-alloy

steels) designating the division (product form) of the standard. This letter is followed by a series of
numbers and letters that indicate the specific steel.
British standards (BS) are developed by the British Standards Institute in London, England. Similar to
the JIS standards, each British designation includes a product form and an alloy code.
AFNOR standards are developed by the Association Francaise de Normalisation in Paris, France. The
correct format for reporting AFNOR standards is as follows. An uppercase NF is placed to the left of the
alphanumeric code. This code consists of an uppercase letter followed by a series of digits, which are
subsequently followed by an alphanumeric sequence.
UNI standards are developed by the Ente Nazionale Italiano di Unificazione in Milan, Italy. Italian
standards are preceded by the uppercase letter UNI followed by a four-digit product form code
subsequently followed by an alphanumeric alloy identification.
Swedish standards (SS) are prepared by the Swedish Standards Institution in Stockholm. Designations
begin with the letters SS followed by the number 14 (all Swedish carbon and low-alloy steels are covered
by SS14). What subsequently follows is a four digit numerical sequence similar to the German Werkstoff
number.

Steel-making processes
Abstract: Steel is made by the Bessemer, Siemens Open Hearth, basic oxygen furnace, electric arc,
electric high-frequency and crucible processes. In both the Acid Bessemer and Basic Bessemer (or
Thomas) processes molten pig iron is refined by blowing air through it in an egg-shaped vessel, known as
a converter, of 15-25 tonnes capacity. In the Siemens process, both acid and basic, the necessary heat for
melting and working the charge is supplied by oil or gas.
Both the gas and air are preheated by regenerators, two on each side of the furnace, alternatively heated
by the waste gases. The regenerators are chambers filled with checker brickwork, brick and space
alternating. The high nitrogen content of Bessemer steel is a disadvantage for certain cold forming
applications and continental works have, in recent years, developed modified processes in which oxygen
replaces air.
Steel is made by the Bessemer, Siemens Open Hearth, basic oxygen furnace, electric arc, electric highfrequency and crucible processes.
Crucible and high-frequency methods
The Huntsman crucible process has been superseded by the high frequency induction furnace in which the
heat is generated in the metal itself by eddy currents induced by a magnetic field set up by an alternating
current, which passes round water-cooled coils surrounding the crucible. The eddy currents increase with
the square of the frequency, and an input current which alternates from 500 to 2000 hertz is necessary. As
the frequency increases, the eddy currents tend to travel nearer and nearer the surface of a charge (i.e.
shallow penetration). The heat developed in the charge depends on the cross-sectional area which carries
current, and large furnaces use frequencies low enough to get adequate current penetration.
Automatic circulation of the melt in a vertical direction, due to eddy currents, promotes uniformity of
analysis. Contamination by furnace gases is obviated and charges from 1 to 5 tonnes can be melted with
resultant economy. Consequently, these electric furnaces are being used to produce high quality steels,
such as ball bearing, stainless, magnet, die and tool steels.

Figure 1.
Furnaces used for making pig iron and steels. RH side of
open hearth furnace shows use of oil instead of gas
Acid and basic steels
The remaining methods for making steel do so by removing impurities from pig iron or a mixture of pig
iron and steel scrap. The impurities removed, however, depend on whether an acid (siliceous) or basic
(limey) slag is used. An acid slag necessitates the use of an acid furnace lining (silica); a basic slag, a
basic lining of magnesite or dolomite, with line in the charge. With an acid slag silicon, manganese and
carbon only are removed by oxidation, consequently the raw material must not contain phosphorus and
sulphur in amounts exceeding those permissible in the finished steel.
In the basic processes, silicon, manganese, carbon, phosphorus and sulphur can be removed from the
charge, but normally the raw material contains low silicon and high phosphorus contents. To remove the
phosphorus the bath of metal must be oxidised to a greater extent than in the corresponding acid process,
and the final quality of the steel depends very largely on the degree of this oxidation, before deoxidisersferro-manganese, ferro-silicon, aluminium-remove the soluble iron oxide and form other insoluble oxides,
which produce non-metallic inclusions if they are not removed from the melt:
2Al + 3FeO (soluble) 3Fe + Al2O3 (solid)
In the acid processes, deoxidation can take place in the furnaces, leaving a reasonable time for the
inclusions to rise into the slag and so be removed before casting. Whereas in the basic furnaces,
deoxidation is rarely carried out in the presence of the slag, otherwise phosphorus would return to the
metal. Deoxidation of the metal frequently takes place in the ladle, leaving only a short time for the
deoxidation products to be removed. For these reasons acid steel is considered better than basic for certain
purposes, such as large forging ingots and ball bearing steel. The introduction of vacuum degassing
hastened the decline of the acid processes.
Bessemer steel
In both the Acid Bessemer and Basic Bessemer (or Thomas) processes molten pig iron is refined by
blowing air through it in an egg-shaped vessel, known as a converter, of 15-25 tonnes capacity (Fig. 1).
The oxidation of the impurities raises the charge to a suitable temperature; which is therefore dependent
on the composition of the raw material for its heat: 2% silicon in the acid and 1,5-2% phosphorus in the
basic process is normally necessary to supply the heat. The "blowing" of the charge, which causes an

intense flame at the mouth of the converter, takes about 25 minutes and such a short interval makes exact
control of the process a little difficult.
The Acid Bessemer suffered a decline in favour of the Acid Open Hearth steel process, mainly due to
economic factors which in turn has been ousted by the basic electric arc furnace coupled with vacuum
degassing.
The Basic Bessemer process is used a great deal on the Continent for making, from a very suitable pig
iron, a cheap class of steel, e.g. ship plates, structural sections. For making steel castings a modification
known as a Tropenas converter is used, in which the air impinges on the surface of the metal from side
tuyeres instead of from the bottom. The raw material is usually melted in a cupola and weighed amounts
charged into the converter.
Open-hearth processes
In the Siemens process, both acid and basic, the necessary heat for melting and working the charge is
supplied by oil or gas. But the gas and air are preheated by regenerators, two on each side of the furnace,
alternatively heated by the waste gases. The regenerators are chambers filled with checker brickwork,
brick and space alternating.
The furnaces have a saucer-like hearth, with a capacity which varies from 600 tonnes for fixed, to 200
tonnes for tilting furnaces (Fig. 1). The raw materials consist essentially of pig iron (cold or molten) and
scrap, together with lime in the basic process. To promote the oxidation of the impurities iron ore is
charged into the melt although increasing use is being made of oxygen lancing. The time for working a
charge varies from about 6 to 14 hours, and control is therefore much easier than in the case of the
Bessemer process.
The Basic Open Hearth process was used for the bulk of the cheaper grades of steel, but there is a
growing tendency to replace the OH furnace by large arc furnaces using a single slag process especially
for melting scrap and coupled with vacuum degassing in some cases.
Electric arc process
The heat required in this process is generated by electric arcs struck between carbon electrodes and the
metal bath (Fig. 1). Usually, a charge of graded steel scrap is melted under an oxidising basic slag to
remove the phosphorus. The impure slag is removed by tilting the furnace. A second limey slag is used to
remove sulphur and to deoxidise the metal in the furnace. This results in a high degree of purification and
high quality steel can be made, so long as gas absorption due to excessively high temperatures is avoided.
This process is used extensively for making highly alloyed steel such as stainless, heat-resisting and highspeed steels.
Oxygen lancing is often used for removing carbon in the presence of chromium and enables scrap
stainless steel to be used. The nitrogen content of steels made by the Bessemer and electric arc processes
is about 0,01-0,25% compared with about 0,002-0,008% in open hearth steels.
Oxygen processes
The high nitrogen content of Bessemer steel is a disadvantage for certain cold forming applications and
continental works have, in recent years, developed modified processes in which oxygen replaces air. In
Austria the LID process (Linz-Donawitz) converts low phosphorus pig iron into steel by top blowing with
an oxygen lance using a basic lined vessel (Fig. 2b). To avoid excessive heat scrap or ore is added. High
quality steel is produced with low hydrogen and nitrogen (0,002%). A further modification of the process
is to add lime powder to the oxygen jet (OLP process) when higher phosphorus pig is used.

Figure 2.
The Kaldo (Swedish) process uses top blowing with oxygen together with a basic lined rotating (30
rev/min) furnace to get efficient mixing (Fig. 2a). The use of oxygen allows the simultaneous removal of
carbon and phosphorus from the (P, 1,85%) pig iron. Lime and ore are added. The German Rotor process
uses a rotary furnace with two oxygen nozzles, one in the metal and one above it (Fig. 2c). The use of
oxygen with steam (to reduce the temperature) in the traditional basic Bessemer process is also now
widely used to produce low nitrogen steel. These new techniques produce steel with low percentages of
N, S, P, which are quite competitive with open hearth quality.
Other processes which are developing are the Fuel-oxygen-scrap, FOS process, and spray steelmaking
which consists in pouring iron through a ring, the periphery of which is provided with jets through which
oxygen and fluxes are blown in such a way as to "atomise" the iron, the large surface to mass ratio
provided in this way giving extremely rapid chemical refining and conversion to steel.
Vacuum degassing is also gaining ground for special alloys. Some 14 processes can be grouped as stream,
ladle, mould and circulation (e.g. DH and RH) degassing methods, Fig. 3. The vacuum largely removes
hydrogen, atmospheric and volatile impurities (Sn, Cu, Pb, Sb), reduces metal oxides by the C O
reaction and eliminates the oxides from normal deoxidisers and allows control of alloy composition to
close limits. The clean metal produced is of a consistent high quality, with good properties in the
transverse direction of rolled products. Bearing steels have greatly improved fatigue life and stainless
steels can be made to lower carbon contents.

Figure 3. Methods of degassing molten steel

Vacuum melting and ESR. The aircraft designer has continually called for new alloy steels of greater
uniformity and reproducibility of properties with lower oxygen and sulphur contents. Complex alloy
steels have a greater tendency to macro-segregation, and considerable difficulty exists in minimising the
non-metallic inclusions and in accurately controlling the analysis of reactive elements such as Ti, Al, B.
This problem led to the use of three processes of melting.

(a) Vacuum induction melting within a tank for producing super alloys (Ni and Co base), in some cases
for further remelting for investment casting. Pure materials are used and volatile tramp elements can be
removed.
(b) Consumable electrode vacuum arc re-melting process (Fig. 4) originally used for titanium, was found
to eliminate hydrogen, the A and V segregates and also the large silicate inclusions. This is due to the
mode of solidification. The moving parts in aircraft engines are made by this process, due to the need for
high strength cleanness, uniformity of properties, toughness and freedom from hydrogen and tramp
elements.
(c) Electroslag refining (ESR) This process, which is a larger form of the original welding process, remelts a preformed electrode of alloy into a water-cooled crucible, utilising the electrical resistance heating
in a molten slag pool for the heat source (Fig. 5). The layer of slag around the ingot maintains vertical
unidirectional freezing from the base. Tramp elements are not removed and lead may be picked up from
the slag.

Figure 4.
Typical vacuum arc remelting furnace

Figure 5.
Electroslag remelting furnace

Clean Steel: Part One

Abstract: Steel cleanliness is an important factor of steel quality and the demand for cleaner steels
increases every year. The so-called clean steel generally is the steel in which the content of impurity
elements, such as phosphorus, sulphur, total oxygen, nitrogen, hydrogen (including carbon sometimes)
and inclusions are very low. The improvement of steel cleanliness has therefore become a more and more
important subject in the development of ferrous metallurgical technology, and also an important task for
the iron and steel producers.
Steel cleanliness is an important factor of steel quality and the demand for cleaner steels increases every
year. The so-called clean steel generally is the steel in which the content of impurity elements, such as
phosphorus, sulphur, total oxygen, nitrogen, hydrogen (including carbon sometimes) and inclusions are
very low. The improvement of steel cleanliness has therefore become a more and more important subject
in the development of ferrous metallurgical technology, and also an important task for the iron and steel
producers.
The demand for better mechanical properties of steels was urging steel producers to improve cleanliness
of their final products. In order to obtain the satisfactory cleanliness of steel it is necessary to control and
improve a wide range of operating practices throughout the steelmaking processes like deoxidant- and
alloy additions, secondary metallurgy treatments, shrouding systems and casting practice.
Due to the vague nature of the term "clean steel", some authors imply that it is more precise to refer to:

steels with low levels of solutes as "high purity steels"

steels with low levels of impurities that originate from the re-melting scrap as "low residual steels"
steels with a low frequency of product defects that can be related to the presence oxides as "clean
steels".

It has been well known that the individual or combined effect of carbon [C], phosphorus [P], sulphur [S],
nitrogen [N], hydrogen [H] and total oxygen (T.O.) in steel can have a remarkable influence on steel
properties, such as tensile strength, formability, toughness, weldability, cracking-resistance, corrosionresistance, fatigue-resistance, etc. Also, clean steel requires control of non-metallic oxide inclusions and
controlling their size distribution, morphology and composition.
The control of the elements mentioned above is different for different performance demands. Those
impurity elements also vary with different grades of steel. Table 1 lists the influence of common steel
impurities on steel mechanical properties which means that some element is harmful to certain steel
grades, but may be less harmful or even useful to another steel grades.
For examples for IF steels, the content of carbon, nitrogen, total oxygen and inclusions should be as low
as possible in order to get good flexibility, high "r" value, perfect surface quality etc. In other hands the
high quality pipeline steel requires ultra low sulphure, low phosphorus, low nitrogen, low total oxygen
content and a certain ratio of Ca/S.
Element

S, O

Form

Sulfide and oxide inclusions

Solid solution

Solid solubility (enhanced), hardenability

Settled dislocation

Strain aging (enhanced), ductility and toughness (lowered)

C, N Pearlite and cementite

Carbide and nitride
precipitates
P

Mechanical Properties Affected

Ductility, Charpy impact value, anisotropy
Formability (elongation, reduction of area and bendability)
Cold forgeability, drawability
Low temperature toughness
Fatigue strength

Dispersion (enhanced), ductility and toughness (lowered)

Precipitation, grain refining (enhanced), toughness
(enhanced)
Embrittlement by intergranular precipitation

Solid solubility (enhanced), hardenability (enhanced)

Solid solution
Temper brittleness
Separation, secondary work embrittlement
Table 1: Influence of typical impurities on mechanical properties

As we mentioned before, steel cleanliness depends on the amount, morphology and size distribution of
non-metallic inclusions. The inclusions generate many defects and many applications restrict the
maximum size of inclusions so the size distribution of inclusions in steel products is also important. For
certain applications where stringent mechanical properties are required the internal cleanliness of steel is
very important. Table 2 shows the cleanliness requirements for various steel grades.
Steel product
IF steels
Automotive and deep-drawing
Sheets
Drawn and Ironed cans
Alloy steel for Pressure vessels

Maximum allowed impurity

fraction

Maximum allowed inclusion

size

[C]30 ppm, [N]40 ppm, T.O.40

ppm
[C]10 ppm, [N]50 ppm
[C]30 ppm, [N]30 ppm

100 m

[C]30 ppm, [N]40 ppm, T.O.20

ppm

20 m

[P]70 ppm

[H]2 ppm, [N]20 ppm, T.O.10

ppm

Alloy steel bars

HIC resistant steel sour gas tubes

[P]50 ppm, [S] 10 ppm

[S]30 ppm, [N]50 ppm, T.O.30
ppm

Line pipes

100 m

Sheets for continuous annealing

[N]20 ppm

Plates for welding

[H]1.5 ppm

Bearings

T.O.10 ppm

15 m

Tire cord

[H]2 ppm, [N]40 ppm, T.O.15

ppm

10 m

Non-grain-orientated Magnetic
Sheets
Heavy plate steels
Wires

[N]30 ppm
[H]2 ppm, [N]=30-40 ppm, T.O.20
ppm

Single inclusion 13 m
Cluster 200 m

[N]60 ppm, T.O.30 ppm

Table 2: Cleanliness requirements for various steel grades

20 m

As Table 2 shows for sheets used for car body, carbon [C], nitrogen [N], and total oxygen (T.O.) are each
required to be very low. For sheets for tin plate application, total oxygen is not only needed below 20
ppm, but the size of the non-metallic inclusions in steel has to be less than 20 m.
For steel cord used in tires, the size of non-metallic inclusions in steel has to be less than 10 m and even
smaller (5 m) for TV shadow masks. For ball bearings, in order to improve their fatigue-resistance
properties, T.O. in steel has to be below 10 ppm and the size of non-metallic inclusions has to be less than
15 m. For meeting the specification of increasingly improved toughness for petroleum pipeline and of
Hydrogen Induced Cracking (HIC) resistance for the transport of sour natural gas, the sulphur [S] content
in steel has to be extremely low, less than 10 ppm.
Steel cleanliness is controlled by a wide range operating practices throughout the steelmaking processes.
These include the time and location of deoxidant and alloy additions, the extent and sequence of
secondary metallurgy treatments, stirring and transfer operations, shrouding systems, tundish geometry
and practices, the absorption capacity of the various metallurgical fluxes, and casting practices.
A one of the steelmaking process routes for the production of clean steels is outlined in Figure 1.

Figure 1: The process route for the production of clean steels

Clean Steel: Part Two

Abstract: Non-metallic inclusions, which are undesirable components of all steels, play an important role
with respect to their effect on the steel properties. Controlling inclusions in steel is closely connected with
the concept of "clean steel". The improvement in steel properties by control of non-metallic inclusions
plays an important part in defending the applications of steel against newer competitive materials.
Non-metallic inclusions, which are undesirable components of all steels, play an important role with
respect to their effect on the steel properties. Controlling inclusions in steel is closely connected with the
concept of clean steel. The improvement in steel properties by control of non-metallic inclusions plays
an important part in defending the applications of steel against newer competitive materials. The aims of
the metallurgist are to eliminate undesirable inclusions and control the nature and distribution of the
remainder to optimize the properties of the final product.
Generally, non-metallic inclusions in steel normally have a negative contribution to the mechanical
properties of steel, since they can initiate ductile and brittle facture. Among various types of nonmetallic
inclusions, oxide and sulphide inclusions have been thought harmful for common steels.
All steels contain non-metallic inclusions to a greater or less extent. The type and appearance of these
non-metallic inclusions depends on factors such as grade of steel, melting process, secondary metallurgy
treatments and casting of steel. Because of this, it is of particular significance to determine how pure the
steel is. The term steel cleanness is relative one, since even steel with only 1 ppm each of oxygen and
sulfide will still contains 109 -1012 non-metallic inclusions per ton. From the viewpoint of cleanness all
steels are dirty.
Non metallic inclusions in steel are the cause for dangerous and serious material defects such as
brittleness and a vide variety of crack formations. However, some of these inclusions can also have a
beneficial effect on steels properties by nucleating acicular ferrite during the austenite to ferrite phase
transformation especially in low carbon steels. According to definition, the non-metallic inclusions are
chemical compounds of metal with nonmetal which are present in steel and alloys like separated parts.

Classification of non-metallic inclusions

Non-metallic inclusions are divided by chemical and mineralogical content, by stableness/stability and
origin. By chemical content non-metallic inclusions are divided into the following groups:
Oxides (simple: FeO, MnO, Cr2O3, TiO2, SiO2, Al2O3 etc.; compound: FeOFe2O3, FeOAl2O3,
MgOAl2O3, FeOCr2O3 etc.)
Sulphides (FeS, MnS, CaS, MgS, Al2S3 etc.; compound: FeSFeO, MnSMnO etc.)
Nitrides (simple: TiN, AlN, ZrN, CeN etc.; compound: Nb(C,N), V(C,N) etc, which can be found
in alloyed steels and has strong nitride-generative elements in its content: titanium, aluminum,
vanadium, cerium etc.)
Phosphides (Fe3P, Fe2P etc.)
The majority of inclusions in steels are oxides and sulphides. Among various types of nonmetallic
inclusions, oxide and sulphide inclusions have been thought harmful for common steels. Usually, nitrides
are present in special steels (stainless steels, tool steels) which have elements with a strong affinity for
nitrogen (e.g. chrome, vanadium), which create nitrides.
Figure 1 shows sulfides and oxides of non metallic inclusion in steel.

Figure 1: Non-metallic inclusion in steel: oxides-dark gray and sulfides-light gray

By mineralogical content oxygen inclusions are divided into the following groups:

Free oxides FeO, MnO, Cr2O3, SiO2 (quartz), Al2O3 (corundum) etc.
Spinels-compound oxides which are formed by bi- and tri-valent elements as a ferrites, chromites
and aluminates.
Silicates which are presented in steel like a glass formed with pure SiO2 or SiO2 with admixture of
iron, manganese, chromium, aluminum and tungsten oxides and also crystalline silicates.

Depending on the melting temperature, in liquid steel non-metallic inclusions are in solid or liquid
condition.
As mentioned above the majority of inclusions in steels are oxides and sulfides. Sulfides in steel have
been paid much attention because their treatment is an important problem in the steelmaking process.
They affect on the properties of the final products by their deformation during the steel working process;
especially their morphology has a significant effect on the steel properties.
According to analysis based on the steel ingots containing 0.01-0.15% S, the morphology of MnS can be
classified into three types:
1) Type I is a globular .MnS with a wide range of sizes, and is often duplex with oxides.
2) Type II has a dendritic structure and is often called grain-boundary sulfide because it is distributed as
chain-like formation or thin precipitates in primary ingot grain boundaries.
3) Type III is angular sulfide and always forms as monophase inclusion.
Most of the above mentioned sulfides are formed both during the process of secondary metallurgy or the
solidification process. Recently, with the development of steelmaking technology, the sulfur concentration
in steel was lowered drastically. Also, the continuous casting technology of steels with higher cooling rate
than the ingot casting almost replaced the ingot casting.
So, the sulfides in the modern commercial steel are usually formed on solidification process or in solid
steel during the subsequent cooling process. For example, the Widmansttten plate-like MnS2, is formed
in solid steel and Figure 2 shows the common morphology of MnS in conventional continuously casting
steel, including the globular duplex oxidesulfide (particle A, B and C) and the Widmansttten plate-like
MnS (particle D).

Figure 2: Typical duplex oxidesulfide inclusion (particle A, B and C) and plate-like MnS (particle
D) in conventional continuous casting silicon steel.
Numerous examples of the effect of non-metallic inclusions on steel properties show the importance of
the behavior of the inclusions as well as of surrounding metal matrix during plastic working of steels. The
aims of the metallurgist are to eliminate undesirable inclusions and control the nature and distribution of
the remainder to optimize the properties of the final product.
An attempt by using program ABACUS was performed to model the behavior of slag inclusions and their
surrounding matrix material during hot rolling and hot forging of hardenable steels. It is shown that it can
be helpful for studying the behavior of inclusions, which is difficult or even impossible to obtain from a
conventional experiment.
Figure 3 shows the effective strain contour during plastic deformation. Three regions of strain
concentration (red) can be seen and a trihedral void (white region) close to the round inclusion is formed.
The strain concentrations arise at the inner surface of the matrix. Another interested thing is that two
edges of the pore tend to emerge and a bonding is formed. The difference in mechanical properties
between the matrix and the inclusion is found to be the primary reason to create a void. The weak
bonding at the interface between the matrix and the inclusion seems to facilitate to open the void.
Figure 4 shows the effect of rolling temperature on the relative plasticity index during hot rolling of
steels. The relative plasticity index of inclusion increases while the rolling temperature rises. There exists
a transition region, where the relative plasticity index changes rapidly. This trend agrees with the existing
experimental results.

Figure 3: Void formation close to the inclusion.

Figure 4: Effects of rolling temperature on the relative plasticity index.

Clean Steel: Part Three

Abstract: The presence of non-metallic oxide inclusions is a major cause of incompatibility between the
attainable and desirable level of cleanliness in many grades of commercial steel. Generally, inclusions
degrade the mechanical properties of the steel and thereby reduce the ductility of the cast metal and
increase the risk for mechanical and/or corrosion failure of the final product.
The increasing demand in recent years for high-quality steel products has led to the continuous
improvement of steelmaking practices. There is a special interest in the control of non-metallic inclusions
due to their harmful effect on the subsequent stages and their great influence on the properties of the final

product. Through the control of the amount, size and chemical composition of the inclusions it is possible
to obtain a final product of good quality. The control of the formation of non-metallic inclusions and the
identification of their constituent phases are of extreme importance for the obtaining of clean steels.
The presence of non-metallic oxide inclusions is a major cause of incompatibility between the attainable
and desirable level of cleanliness in many grades of commercial steel. Generally, inclusions degrade the
mechanical properties of the steel and thereby reduce the ductility of the cast metal and increase the risk
for mechanical and/or corrosion failure of the final product.
Oxide inclusions originate from two sources:

residual products resulting from intentionally added alloying elements to deoxidize the molten
steel after oxygen treatment (endogenous or micro inclusions);
products resulting from reactions between the melt and atmosphere, slag, or refractory (exogenous
or macro inclusions).

Among various types of nonmetallic inclusions, oxide and sulphide inclusions have been thought harmful
for common steels.
Alumina inclusions occur as deoxidation products in the aluminum-based deoxidation of steel. Pure
alumina has a melting point above 2000C, i.e., these alumina inclusions are present in a solid state in
liquid steel. The addition of calcium to steel which contains such inclusions changes the composition of
these inclusions from pure alumina to CaO-containing calcium aluminates.
As it can be see from Figure 1, the, melting point of the calcium aluminates will decrease as the CaO
content increases, until liquid oxide phases occur at about 22% of CaO, i.e., when the CaO.2Al2O3
compound is first exceeded at 1600C. The liquid phase content continues to increase as CaO content
rises further and is 100% at 35% of CaO. The minimum melting temperature for the liquid calcium
aluminates is around 1400C, i.e., such liquid calcium aluminates may be present in liquid form until, or
even after, the steel solidifies.
Most grades of steel are treated with calcium using either a Ca-Si alloy or a Ca-Fe(Ni) mixture,
depending on the silicon specification. This treatment is made after trim additions and argon rinsing.
In most melt shops the cored wire containing Ca-Si or Ca-Fe(Ni) injection system is used in the calcium
treatment of steel. The melting and boiling points of calcium are 839C and 1500C respectively. During
calcium treatment, the alumina and silica inclusions are converted to molten calcium aluminates and
silicate which are globular in shape because of the surface tension effect. The change in inclusion
composition and shape is known as the inclusion morphology control.

Figure 1: Binary system CaO-Al2O3

The calcium aluminates inclusions retained in liquid steel suppress the formation of MnS stringers during
solidification of steel. This change in the composition and mode of precipitation of sulphide inclusion
during solidification of steel is known as sulphide morphology or sulphide shape control.
Several metallurgical advantages are brought about with the modification of composition and morphology
of oxide and sulphide inclusions by calcium treatment of steel, as for instance:

To improve steel castability in continuous casting, i.e. minimize nozzle blockage

To minimize inclusion related surface defects in billet, bloom and slab castings
To improve steel machinability at high cutting speeds and prolong the carbide tool life
To minimize the susceptibility of steel to re-heat cracking, as in the heat-affected zones (HAZ) of
welds
To prevent lamellar tearing in large restrained welded structures
To minimize the susceptibility of high-strength low alloy (HSLA) linepipe steels to hydrogeninduced cracking (HIC) in sour gas or sour oil environments. The Ca content in the final product
can be controlled within the range of 15 to 20 ppm
To increase both tensile ductility and impact energy in the transverse and through-thickness
directions in steels with tensile strengths below 1400 MPa

When calcium is injected deep into the melt, the following series of reactions are expected to occur to
varying extents in Al-killed steels containing alumina inclusions:
Ca + O = CaO

(1)

Ca + S = CaS

(2)

Ca + (x+1/3)Al2O3 = CaOx Al2O3 + 2/3[Al]

(3)

Depending on the steel composition, the manner of calcium adding in steel bath and other process
variables, there will be variations in the conversion of alumina inclusions to aluminates inclusions, the
smaller inclusions will be converted to molten calcium aluminates more readily than the larger inclusions.
Thermodynamically, if sulfur or oxygen is dissolved in the steel at moderate levels, or if Al2O3 inclusions
are present in steel, calcium will react with oxygen or sulfur until the contents of reactants are very low (<
2ppm). One of the critical questions is whether or not calcium added to steel will react with sulfur by
reaction (2) and form CaS or modify Al2O3 to liquid calcium aluminates by reaction (3).
The formation of calcium sulfide can occur if calcium and sulfur contents are sufficiently high. Since
calcium has higher affinity for oxygen than for sulfur, the addition of calcium initially results in a more or
less pronounced conversion of the alumina into calcium aluminates until the formation of calcium
sulfides starts as the addition of calcium continues.
Calcium sulfides are solid at steelmaking temperatures and result in nozzle clogging similar to that caused
by alumina. As can be observed from the Figure 2, the conversion of alumina into calcium aluminates
occurs until all the inclusions in the steel are present only in liquid form.

Figure 2: Change of inclusions composition during calcium additions

To prevent nozzle clogging in continuous casting by solid inclusions, calcium is added to steel to modify
inclusions and desulfurize the steel. Calcium will convert solid alumina (Al2O3) inclusions into lower
melting point calcium aluminates, which will help prevent the clogging of the casting nozzles. However,
when calcium is added to steel, it will also react with oxygen and sulfur and modify the sulfide inclusions.
If the sulfur content of the steel is high, calcium will react with sulfur forming solid CaS, which could
clog up the continuous casting nozzle.
The Figure 3 shows influence of calcium treatment on the type of inclusions formed and its relationship
with nozzle clogging.

Figure 3: Influence of calcium treatment on the type of inclusions formed and its relationship with
nozzle clogging
Calcium treatment cannot be applied to all kinds of steel. For those with high requirement on formability,
such as automobile sheet, calcium treatment is not suitable, because this treatment causes the formation of
calcium aluminates inclusion which is hard. Therefore, for those kinds of steel, the method of improving
molten steels purity is usually taken to optimize castability. Through controlling carry-over slag from
melting furnace, deformation treatment of ladle slag, metallurgy in tundish, protective casting and other
measures, purity of steel is guaranteed and total oxygen content in molten steel decreases.

Nitrogen in Steels: Part One

Abstract: All steels contain some nitrogen which is effective in improving the mechanical and corrosion
properties of steels if it remains in solid solution or precipitates as very fine and coherent nitrides. When
nitrogen is added to austenitic steels it can simultaneously improve fatigue life, strength, work hardening
rate, wear and localized corrosion resistance.
High nitrogen martensitic stainless steels show improved resistance to localized corrosion (pitting, crevice
and intergranular corrosion) over their carbon containing counterparts. Because of this, the high nitrogen
steels are being considered a new promising class of engineering materials.
All steels contain some nitrogen which is effective in improving the mechanical and corrosion properties
of steels if it remains in solid solution or precipitates as very fine and coherent nitrides. When nitrogen is
added to austenitic steels it can simultaneously improve fatigue life, strength, work hardening rate, wear
and localized corrosion resistance.
High nitrogen martensitic stainless steels show improved resistance to localized corrosion (pitting, crevice
and intergranular corrosion) over their carbon containing counterparts. Because of this, the high nitrogen
steels are being considered a new promising class of engineering materials.

Solubility of Nitrogen
The nitrogen solubility data are summarized by the following equations and are shown graphically in
Fig.1
N2=[N]

(1)

The equilibrium constant for nitrogen absorption is therefore:

K=[ppmN] / (pN2)

(2)

And reaction constant of this equation is related to the free energy;

(3)
which becomes zero in case of equilibrium leading to:

(4)
If it is assume that the activity of the nitrogen dissolved in the steel is approximately the same as the
chemical concentration (Henry's law), then this concentration can be calculated as:
[%N]=KN(pN2)

(5)

Sources of Nitrogen in Steelmaking

Numerous sources of nitrogen exist during the melting, the ladle processing and the casting operations.
Sources of nitrogen in oxygen steelmaking include the hot metal, the scrap, the impurity nitrogen in
oxygen and the nitrogen used as a stirring gas.
Nitrogen pickup from the atmosphere can occur during reblows in which case the furnace fills up with
air, which is then entrained into the metal when the oxygen blow restarts. Also during the tapping of steel,
air bubbles are entrained into the steel where the tap stream enters the bath in the ladle. Other sources
may include atmosphere (through ladle slag), coke (carburizers) and various ferro-alloys. Ladle additions
often contain moisture. The otherwise, to get an impression of the sources of nitrogen during the melting
process, Table 1 shows the amount of nitrogen present in each of the feed materials typically used in the
EAF.
Table 1: Nitrogen content of feed materials used in EAF steelmaking
Feed Material
Nitrogen Content
Scrap

30-120 ppm

HBI/DRI

20-30 ppm

Liquid iron from the BF 60 ppm

Cold pig iron (CPI)

20-30 ppm

Hot heel

10 ppm

Coke

5000-10000 ppm

Oxygen

30-200 ppm

Carbon Carrier Gas (Air) 78%

Bottom stirring gas(N2) > 99,9%
Bottom stirring gas (Ar) < 30 ppm
CaO

400 ppm

Behavior of Nitrogen in Steel

While steel is liquid the nitrogen present exists in the solution. However, solidification of steel may result
in three nitrogen-related phenomena: formation of blowholes; precipitation of one or more nitride
compounds; and/or the solidification of nitrogen in interstitial solid solution.
The maximum solubility of nitrogen in liquid iron is approximately 450 ppm, and less than 10 ppm at
ambient temperature, as shown in Figure 1. The presence of significant quantities of other elements in
liquid iron affects the solubility of nitrogen. More importantly, the presence of dissolved sulfur and
oxygen limit the absorption of nitrogen because they are surface-active elements. This is exploited during
steelmaking to avoid excessive nitrogen pickup, particularly during tapping.

Figure 1: Solubility of nitrogen in iron for temperatures of 600-2000C

Effect of Nitrogen on Steel Properties

The effect of nitrogen on steel properties can be either detrimental or beneficial, depending on the other
alloying elements present, the form and quantity of nitrogen present, and the required behavior of the
particular steel product.
In general, however, most steel products require that nitrogen be kept to a minimum. High nitrogen
content may result in inconsistent mechanical properties in hot-rolled products, embrittlement of the heat
affected zone (HAZ) of welded steels, and poor cold formability. In particular, nitrogen can result in strain
ageing and reduced ductility of cold-rolled and annealed LCAK steels.

Effect of Nitrogen on Formability

Figure 2 shows that the strength of LCAK steels decreases slightly and then increases with increasing
nitrogen. Conversely, the elongation decreases and the r-value increases with increasing nitrogen. The rvalue is the average ratio of the width to thickness strain of strip tensile specimens tested in various
orientations. It is an inverse measure of formability. Hence, high nitrogen content leads to poor
formability of LCAK steels, even after annealing.

Figure 2: Effect of nitrogen on yield strength, tensile strength, r-value and elongation of LCAK steel in
the annealed condition
The effect of nitrogen on mechanical properties is the result of interstitial solid solution strengthening by
the free nitrogen; precipitation strengthening by aluminum and other nitrides; and grain refinement due to
the presence of nitride precipitates.

Effect of Nitrogen on Hardness

Hardness is the resistance of a material to surface indentation. The Figure 3 shows that hardness increases
linearly with increasing nitrogen content. Nitrogen absorbed during steelmaking results in interstitial solid
solution strengthening and grain refinement, both of which increase hardness. Further, the diagram shows
that nitrogen absorbed during the steelmaking process has a more significant impact than that absorbed
during batch annealing in a nitrogen-rich atmosphere, although both have a measurable effect.

Figure 3: Increase in hardness of aluminum-killed sheet steel with respect to increasing nitrogen content

Effect of Nitrogen on Strain Ageing

Strain ageing occurs in steels containing interstitial atoms, predominantly nitrogen, after they have been
plastically deformed. After deformation, the nitrogen segregates to dislocations causing discontinuous
yielding when further deformed. Not only does strain ageing result in increased hardness and strength,
and reduced ductility and toughness, but it may also result in the appearance of 'fluting' or 'stretcher
strains' on the surface of deformed material. Duckworth and Baird have developed a measure of strain
ageing termed 'strain ageing index'. This is based on an empirical equation to calculate the increase in
yield stress when deformed material is held for 10 days at room temperature. Figure 4 shows that
increasing nitrogen results in a higher stain-ageing index, and therefore greater propensity for surface
defects.

Figure 4: Effect of nitrogen on strain ageing in mild steels with varying manganese content

Effect of Nitrogen on Impact Properties Including Welded Material

The ability of a material to withstand impact loading is commonly known as toughness. It is sometimes
quantified by measuring the amount of energy that is absorbed by a test piece of known dimensions prior
to fracture. It is further analyzed by determining the fracture mechanism upon impact over a range of

temperatures. As temperature is decreased, the fracture type will change from fibrous/ductile to
crystalline/brittle. This arbitrary temperature is termed the 'ductile-to-brittle' transition temperature. The
lower the transition temperature the better the impact properties, since failure via ductile fracture may be
less catastrophic than that via brittle failure. Figure 5 demonstrates that as free nitrogen increases, the
transition temperature increases, and therefore toughness decreases. This is attributed to solid solution
strengthening.

Figure 5: Effect of free nitrogen on impact properties

Conversely, limited amounts of nitrogen present as precipitates have a beneficial effect on impact
properties. Nitrides of aluminum, vanadium, niobium and titanium result in the formation of fine-grained
ferrite. Further, the smaller the grain size the lower the transition temperature, hence improved toughness.
Therefore, it is necessary to carefully control, not only the nitrogen content, but also the form in which it
exists, in order to optimize impact properties. Nitrogen is known to affect the toughness of the heataffected zone (HAZ) of welded steel. This is important, since the weld metal should not be a point of
weakness in a welded structure. This loss in toughness is often referred to as HAZ embrittlement. It is
thought this occurs when the nitrides present in the HAZ are dissociated as a result of the elevated
temperatures that exist during welding. The absence of precipitates results in grains of larger diameter.
Also, the metal cools quickly producing low toughness martensite or bainite, which contain high levels of
free nitrogen further exacerbating the loss of toughness. Using lower heat input and several passes to
prevent dissociation of the nitrides may prevent this.

Nitrogen in Steels: Part Two

Abstract: The effect of nitrogen on mechanical properties is the result of interstitial solid solution
strengthening by the free nitrogen; precipitation strengthening by aluminum and other nitrides; and grain
refinement due to the presence of nitride precipitates.
Nitrogen absorbed during steelmaking results in interstitial solid solution strengthening and grain
refinement, both of which increase hardness.

Effect of Nitrogen on Formability

Figure 1 shows that the strength of LCAK steels decreases slightly and then increases with increasing
nitrogen. Conversely, the elongation decreases and the r-value increases with increasing nitrogen. The rvalue is the average ratio of the width to thickness strain of strip tensile specimens tested in various
orientations. It is an inverse measure of formability. Hence, high nitrogen content leads to poor
formability of LCAK steels, even after annealing.

Figure 1: Effect of nitrogen on yield strength, tensile strength, r-value and elongation of LCAK steel in
the annealed condition
The effect of nitrogen on mechanical properties is the result of interstitial solid solution strengthening by
the free nitrogen; precipitation strengthening by aluminum and other nitrides; and grain refinement due to
the presence of nitride precipitates.

Effect of Nitrogen on Hardness

Hardness is the resistance of a material to surface indentation. The Figure 2 shows that hardness increases
linearly with increasing nitrogen content. Nitrogen absorbed during steelmaking results in interstitial solid
solution strengthening and grain refinement, both of which increase hardness. Further, the diagram shows
that nitrogen absorbed during the steelmaking process has a more significant impact than that absorbed
during batch annealing in a nitrogen-rich atmosphere, although both have a measurable effect.

Figure 2: Increase in hardness of aluminum-killed sheet steel with respect to increasing nitrogen content
Strain ageing occurs in steels containing interstitial atoms, predominantly nitrogen, after they have been
plastically deformed. After deformation, the nitrogen segregates to dislocations causing discontinuous
yielding when further deformed. Not only does strain ageing result in increased hardness and strength,
and reduced ductility and toughness, but it may also result in the appearance of "fluting" or "stretcher
strains" on the surface of deformed material.
Duckworth and Baird have developed a measure of strain ageing termed "strain ageing index". This is
based on an empirical equation to calculate the increase in yield stress when deformed material is held for
10 days at room temperature. Figure 3 shows that increasing nitrogen results in a higher stain-ageing
index, and therefore greater propensity for surface defects.

Figure 3: Effect of nitrogen on strain ageing in mild steels with varying manganese content

Effect of Nitrogen on Impact Properties Including Welded Material

The ability of a material to withstand impact loading is commonly known as toughness. It is sometimes
quantified by measuring the amount of energy that is absorbed by a test piece of known dimensions prior
to fracture. It is further analyzed by determining the fracture mechanism upon impact over a range of
temperatures.

As temperature is decreased, the fracture type will change from fibrous/ductile to crystalline/brittle. This
arbitrary temperature is termed the "ductile-to-brittle" transition temperature. The lower the transition
temperature the better the impact properties, since failure via ductile fracture may be less catastrophic
than that via brittle failure.
Figure 4 demonstrates that as free nitrogen increases, the transition temperature increases, and therefore
toughness decreases. This is attributed to solid solution strengthening.

Figure 4: Effect of free nitrogen on impact properties

Conversely, limited amounts of nitrogen present as precipitates have a beneficial effect on impact
properties. Nitrides of aluminum, vanadium, niobium and titanium result in the formation of fine-grained
ferrite. Further, the smaller the grain size the lower the transition temperature, hence improved toughness.
Therefore, it is necessary to carefully control, not only the nitrogen content, but also the form in which it
exists, in order to optimize impact properties.
Nitrogen is known to affect the toughness of the heat-affected zone (HAZ) of welded steel. This is
important, since the weld metal should not be a point of weakness in a welded structure. This loss in
toughness is often referred to as HAZ embrittlement.
It is thought that this occurs when the nitrides present in the HAZ are dissociated as a result of the
elevated temperatures that exist during welding. The absence of precipitates results in grains of larger
diameter. Also, the metal cools quickly producing low toughness martensite or bainite, which contain high
levels of free nitrogen further exacerbating the loss of toughness. Using lower heat input and several
passes to prevent dissociation of the nitrides may prevent this.

Residual Elements in Steel

Abstract: Residual elements (Cu, Ni, As, Pb, Sn, Sb, Mo, Cr, etc.) are defined as elements which are not
added on purpose to steel and which cannot be removed by simple metallurgical processes. The presence
of residual elements in steel can have strong effects on mechanical properties. There is therefore clearly
the need to identify and to quantify the effects of residual elements in order to keep these effects within
acceptable limits.
Residual elements, or at least some of them, have an influence on processing conditions and regimes,
from casting to the final annealing, and possibly on all mechanical properties.
Residual elements (Cu, Ni, As, Pb, Sn, Sb, Mo, Cr, etc.) are defined as elements which are not added on
purpose to steel and which cannot be removed by simple metallurgical processes. The presence of
residual elements in steel can have strong effects on mechanical properties. There is therefore clearly a

need to identify and to quantify the effects of residual elements in order to keep these effects within
acceptable limits.
Residual elements, or at least some of them, have an influence on processing conditions and regimes,
from casting to final annealing, and possibly on all mechanical properties. A clear distinction has to be
made between those residual elements which have an effect due to their presence in solid solution, such as
Mo, Cr, Ni, and Cu, and those which have an effect due to their segregation at interfaces (surface and
grain boundaries), such as Sn, As, and Sb.
The following non exhaustive list gives some possible metallurgical effects of residual elements on
processing conditions and properties of steel products. Residuals may influence:
1. The processing conditions in terms of:

Recrystallisation and rolling forces in the hot strip mill: Mo, Cr, Sn, ...
Austenite to ferrite transformation, hardenability: All
Hot ductility during hot deformation: Zn, Sn, ...
Recrystallisation during annealing: Mo, Cr, Sn, ...

2. The surface aspect of the hot rolled and pickled strip: Cu, Ni, As, Sn, ...

Due to hot shortness

Due to possible synergy of Cu an Sn in hot shortness

3. The embrittlement of grain boundaries: Sb, Sn, As

During strip coiling

During batch or continuous annealing of low C steels

4. The precipitate/matrix interface segregation phenomena: Sn

Ostwald ripening, precipitate growth, texture control

Sn on Fe4N, Sn on MnS, Sb on TiC, ...

5. The mechanical properties of the final products: All

Hot strips and cold rolled sheets

Plates
Long products

6. The coating by hot dip or electrodeposition

7. The weldability of HSS grades : Mo, Cr, Cu, Ni
Residual elements enter steel from impurities in ore, coke, flux and scrap; from these, scrap is considered
to be the main source of residuals. The most commonly found residuals are Cu, Ni, Cr, Mo, and Sn. The
acceptance limits of these residuals depend mainly on product requirements.
A major problem of the recycling process is to control the level of undesirable elements or residuals
elements in order to ensure the steel cleanness required by the product performance. The most of steels
used today are low carbon/low alloy and extra deep drawing grades of steel. The properties of these steels
are very sensitive to the residual elements content and to the thermomechanical processing.
As far as flat products and reinforcing bars are concerned, Table 1 shows typical values of main residual
elements for the EAF route, in wt%.
Table 1: Mean Residual Element Levels in EAF Produced Steels

Cu
Flat products

Ni

Cr

Mo

Sn

0.050-0.2000 0.050-0.2000 0.025-0.1000 0.010-0.0300 0.010-0.0300

Reinforcing bar max 0.48

max 0.08

max 0.24

max 0.06

max 0.08

Although the effect of residuals on properties may be quite small, sometimes even a small change in some
property can significantly increase the rejection rate of products with specified requirements. The general
consensus about effects of residuals such as Cu, Ni, Cr, Mo, Sn and Sb on various steel properties is given
in Table 2.
Table 2: Effects of increase of residual elements content on various steel properties
Property

Cu

Ni

Cr

Mo

Sn

Sb

Strength and hardness

+,

Ductility

+,

+,

Strain hardening, n

0,

+,

0,

Impact resistance

Hardenability

Weldability

Corrosion resistance

Strain ratio, r

0,
+,0

+,0

Temper embrittlement

(+) Indicates an increase

(-) Indicates a decrease
The strengthening mechanisms in steel include: solid solution strengthening, fine grain size, precipitation,
amount of pearlite, dislocations introduced by cold work, and bainitic and martensitic transformations.
The residuals affect the tensile properties through solid solution strengthening. At the low concentrations
that the these residuals are present, the yield and tensile strength increment due to solid solution may
taken as proportional to solute concentration. Some estimates of strength increments contributed by
various residuals are given in Table 3.
Table 3: Effect of residuals on yield and tensile strength; strength increment per wt%
Base Material and Heat
Treatment

Yield strength, MPa/ksi

Cu

Ni

Cr

Low Carbon Steel

normalized or annealed

41/6

0/0

-27/4

13/2 124/18 13/2

13/2

-34/5 -55/-8

Low Carbon Steel

normalized

76/11

41/6

55/8

55/8

34/5

69/10

0.3 Carbon Steels

normalized

82/12

55/8

62/9

62/9

34/34 89/89 69/10

55/8

89/13

0.2 Carbon Steel as-rolled

Hydrogen in Steels

Mo

Tensile strength, MPa/ksi

13/2

Sn

Cu

Ni

Cr

69/10 131/19

Mo

Sn

Abstract: The control of hydrogen content in steels is an important task of steelmakers because of its
generally detrimental effects on processing characteristics and service performance of steel products. Just
a few parts per million of hydrogen dissolved in steel can cause hairline cracks (flakes), hydrogen
embrittlement, hydrogen blistering and loss of tensile ductility, particularly in large steel castings ingots,
blooms and slabs.
Hydrogen has been and always will be a source of various problems within steel production because of its
generally detrimental effects on processing characteristics and service performance of steel products. If
the hydrogen content of the molten steel exceeds the solubility limit of hydrogen in solid iron, the
hydrogen will be rejected during solidification, and this leads to pinhole formation and porosity in steel.
Just a few parts per million of hydrogen dissolved in steel can cause hairline cracks (flakes), hydrogen
embrittlement, hydrogen blistering and loss of tensile ductility, particularly in large steel castings ingots,
blooms and slabs.

Thermodynamic considerations
According to Sievert's law, a di-atomic gas reacts with a metal and is dissolved into atomic form. In the
case of hydrogen solubility, data are summarized by the following equations and are shown graphically in
Fig 1.
H2(G) = [H] (dissol. in metal)

(1)

The equilibrium constant of reaction (1) is:

K= [ppm H] / (pH2)

(2)

Figure 1: Solubility of Hydrogen in pure iron or low-alloy steel at 1 atm pressure of H2

The temperature dependence of K in iron in equilibrium with pH2 = 1 atm is as follows for , (bcc) iron,
(fcc) iron and liquid iron (I) are given by the following equations:
log K ,= -1418/T+ 1.628

(3)

log K = -1182/T+ 1.628

(4)

log K I = -1900/T+ 2.423

(5)

where the temperature T is in degrees Kelvin.

During rapid cooling of a heavy-section steel casting, e.g. thick slab or bloom, there will be little diffusion
of H out of casting. Because of the hydrogen solubility decreases with a decreasing temperature, there
will be a build up of H2 pressure in the steel matrix during rapid cooling. For the limiting case of no
hydrogen diffusion, the H2 pressures will be as shown below in the steel containing 2, 4 and 8 ppm H.
Table 1: Build up of H2 pressure in the steel matrix during rapid cooling
Temperature, C
H2 pressure, atm

2 ppm H

4 ppm H

8 ppm H

1400

0.058

0.23

0.90

1100

0.12

0.48

1.90

900

0.23

0.92

3.70

900

0.58

2.33

9.30

700

1.83

7.30

29.2

500

10.4

41.6

166.5

Hydrogen pickup
Numerous sources of hydrogen exist during the melting, the ladle processing and the casting operations.
Hydrogen pickup in the steel is primarily due to the water associated with the slagmaking materials and as
an impurity in the alloy additions and the carburizers. Hydrogen is generally not a problem in the BOF
steelmaking except in the bottom blown converters (Q-BOP) where natural gas (CH4), used as a tuyere
coolant, is the major source of hydrogen.
The lime, e.g. calcium oxide (CaO), is an important addition during steelmaking operations, especially
during ladle metallurgy to adjust slag chemistry, to facilitate inclusion removal and for desulphurization
of steels. Due to the moist atmospheric conditions, lime can become hydrated to form calcium hydroxide.
This hydrated lime when added to the liquid melt decomposes according to the reaction
Ca(OH)2(s) = CaO(s) + H2O(g)

(6)

The water vapor formed dissociates on the liquid steel surface causing hydrogen pickup by the following
reaction
H2O(g) = 2[H] + [O]

(7)

Figure 2, 3 and 4 show results of experiments performed in laboratory and on the industrial scale to
investigate the effect of both calcium hydroxide and coke addition on the hydrogen content in carbon
steels.
All figures show the variation of hydrogen pickup as a function of additional Ca(OH)2 and coke. In Figure
2 showed results where is the Ca(OH)2 was added on top of the liquid metal while in Figure 3 showed
results of case that the calcium hydroxide was added along with the CaO-Al2O3 slag. Figure 4 shows the
effect of metallurgical coke addition on the hydrogen content of low carbon steel.

Figure 2: Hydrogen pickup due to Ca(OH)2 addition on the top of the slag

Figure 3: Hydrogen pickup due to Ca(OH)2 addition along with the CaO-Al2O3 slag

Figure 4: Change in the hydrogen content of the liquid metal as a function of coke addition for 90 tone
heat
As a follow up of these trials it can be seen that the hydrogen pickup increases in steel with both addition
of lime e.g. Ca(OH)2 and coke. The capacity of the melt to absorb the hydrogen decreases as the hydrogen
content in the melt approaches the equilibrium value. The capacity to absorb hydrogen increases as the
steel is deoxidized.
The control of hydrogen content in steels is an important task of steelmakers during BOF and EAF
steelmaking. The control of the pickup of hydrogen must include the use of inputs with low moisture or

hydrogen content, avoidance of late addition of lime during smelting process, minimization of carry over
slag, efficient degassing at deep vacuum and intense purging, recarburization with low hydrogen pet coke,
control of ladle slag basicity etc.

Effect of Phosphorus on the Properties of Carbon

Steels: Part One
Abstract: Phosphorus in steel can have beneficial as well as harmful effects. Phosphorus is one of the
most potent solid-solution strengtheners of ferrite. The addition of only 0.17% phosphorus increases both
the yield and tensile strength of low-carbon sheet steel by about 62 MPa (9 ksi) while also improving the
bake hardening response and deep drawability. Because of these properties, rephosphorized high-strength
steels are widely used for cold-forming applications. Phosphorus is also used as an additive in steels to
improve machining characteristics and atmospheric corrosion resistance.
Phosphorus in steel can have beneficial as well as harmful effects. Phosphorus is one of the most potent
solid-solution strengtheners of ferrite. The addition of only 0.17% phosphorus increases both the yield
and tensile strength of low-carbon sheet steel by about 62 MPa (9 ksi) while also improving the bake
hardening response and deep drawability. Because of these properties, rephosphorized high-strength steels
are widely used for cold-forming applications. Phosphorus is also used as an additive in steels to improve
machining characteristics and atmospheric corrosion resistance.
Detrimental effects of phosphorus in steel include various forms of embrittlement which reduce the
toughness and ductility. The most familiar example in this category is the classic phenomenon of temper
embrittlement in heat-treated low-alloy steels resulting from segregation of phosphorus and other
impurities at prior austenite grain boundaries. This form of embrittlement and the contributing role of
certain alloying elements has been a subject of research for several decades.
Two other forms of intergranular embrittlement can occur in steels containing phosphorus in the normal
range of 0.008 to 0.025%. In both types, fracture follows the ferrite grain boundaries (instead of prior
austenite grain boundaries) weakened by the segregation of phosphorus during slow cooling of coiled
strip or during final annealing after cold rolling. In one type, planar-oriented cracking (separation) is
observed in the production of high-strength, low-alloy strip for line pipe. In the other type, brittle fracture
may occur during secondary cold working of sheet steel that has previously been deep drawn (with
elongated ferrite grains creating planes of relative weakness) or during service of the drawn part. As most
texts on metallurgy emphasize, phosphorus also increases the hardenability of steel.
Several studies have demonstrated that although the magnitudes of the effects observed vary considerably.
The most common method for calculating hardenability from steel composition as outlined in standards
ASTM A255 and SAE J406 does not consider the effect of phosphorus. The explanation for this omission
is that the effects of phosphorus and sulfur in residual amounts tend to cancel one another. Because of its
detrimental effects on toughness and ductility of heat-treated steels, phosphorus addition is generally not
employed for increasing hardenability. Table 1 summarizes the effect of phosphorus on the properties of
various grades of steel.
Table 1: Summary of the effects of phosphorus on the properties of various steel grades.
PROPERTY
EFFECT
Strength

Strong increase

Bake hardenabillity

Increase

Ductility

Strong decrease

Texture (R-value)

Depends on composition and processing

Coating behavior:
Fe-Zn Galvanneal

Demands control of phosphorus. Can improve powdering.

Phosphatability

May improve

Enameling steels

Improves fishscaling. Accelerates pickling.

Spot weldability

Not harmful up to ~0.1%

Core loss of motor lamination steel Strong decrease (improvement)

Embrittlement

Aggravates

Very low Phosphorus

The P requirement for this category ranges up to about 0.02%. Steels with very low maximum
phosphorus requirements include those that are particularly susceptible to embrittlement. These are
mainly high-strength, low-alloy steels containing, for example: Mn, Si, Ti, Nb, V, Mo, Cr, etc.
While most attention seems to have been focused on residual sulfur reduction, the trend now is to reduce
the levels of all residuals including phosphorus. Line pipe steels are among the most demanding as
regards low phosphorus content. For the transmission of corrosive gases maximum content of phosphorus
P=max 0.02% will be necessary and P=max 0.01% is desirable. The phosphorus content less than 0.01%
will be indispensable for low temperature service.
Demand for higher formability has increased the use of stabilized, ultra-low carbon steels. As mentioned
previously, these steels are susceptible to secondary-work embrittlement in deeply drawn parts. Although
boron additions alleviate this problem, boron exerts a negative impact on formability, Lower phosphorus
levels, below 0.01 percent, represent a potential alternative solution to the secondary work embrittlement
problem.

Moderately Low Phosphorus

Products for which roughly 0.02% to 0.03% phosphorus is tolerable include most low-strength grades and
high-strength steels that are not subject to hostile environments. Whenever high ductility is required,
phosphorus should be kept as low as possible, while keeping in mind the increased cost of reducing the
phosphorus level.
For commercial quality, plain-carbon steels where formability requirements are minimal, the upper limit
of range can be somewhat relaxed. From a product consistency standpoint, tight control of phosphorus is
more important than reducing its level below about 0.02% for steels that fall into this category.

High Phosphorus (Rephosphorized)

Phosphorus is commonly used as a strengthening agent in amounts up to about 0.1%. Also, as much as
0.155% P is added to cold rolled, motor lamination steels to reduce AC core loss.
As discussed previously, many properties are sensitive to the phosphorus content and the effect of
phosphorus depends on the processing method. In addition, processes such as galvanneling are sensitive
to the phosphorus content of the base steel. Therefore, tight control of the phosphorus level and choosing
the proper process route are important if consistent properties are to be obtained and embrittlement
problems avoided.

Strength
Phosphorus is one of the most potent solid solution strengtheners of ferrite. Hence, small additions of
phosphorus are used to inexpensively increase the strength of low carbon sheet steel. Figure 1 compares
the change in lower yield strength of carbon steel as a function of alloy addition for several common
elements.
Among the elements considered, only carbon and nitrogen produce a greater strengthening effect than
phosphorus. This is related to the fact that phosphorus enters the crystal lattice as a substitution solute,

whereas carbon and nitrogen are interstitial solutes in ferrite. Nevertheless, the addition of only 0.1 wt. %
of phosphorus raises the yield strength by about 62 MPa (9 ksi). A similar effect of phosphorus is
observed on ultimate tensile strength. In addition, the strengthening effect of phosphorus does not appear
to be sensitive to the carbon content of the steel.

Figure 1: Change in the lower yield strength of carbon steel as a function of the alloy content for several
common elements (1ton/inch2 = 13.8 MPa)
The effect of grain size on strength is influenced by the phosphorus content in ferrite. By additions of up
to about 0.1 percent of phosphorus, particularly in the case of ultra-low carbon ULC steels with C=max
50 ppm.
Cold working increases the strength of most metals through the process of work hardening (strain
hardening). For an annealed metal, work hardening has a stabilizing influence on plastic deformation
which delays fracture and enhances ductility. Thus, a high capacity for work hardening is important for
products that require high formability.
Phosphorus has a tendency to reduce the work-hardening rate of ferrite. But only a minor decrease in the
strain-hardening exponent, n, with increasing phosphorus up to 0.12 percent was observed by Hu in
laboratory processed low carbon, Al-killed steel. The detrimental effect of P on n is greater in Tistabilized ULC steel. But the n-value of this steel still maintained high levels, in excess of 0.27 even at
0.1 percent of phosphorus. Thus it appears that the work-hardening capacity of ferrite is not seriously
impaired by dilute additions of phosphorus.

Bake Hardening
With proper control of steel composition and processing, an increment in hardening can be induced by
heating certain steels after plastic straining. This effect, known as bake hardening, can be economically
exploited during the plant-bake cycle of formed sheet steel parts in which the peak steel temperature
reaches approximately 170C. Bake hardening is associated with carbon and/or nitrogen strain aging
whereby mobile dislocations are pinned by interstitial atoms pr clusters. Hence, the magnitude of the
bake-hardening effect depends on the amount of carbon and/or nitrogen retained in solid solution after
final processing. In addition, strain aging (and bake hardening) depends on grain size-the effect increase
with decreasing grin size.
The effect of phosphorus on bake hardening in carbon steels has received considerable attention. It is
generally agreed that phosphorus enhances bake hardening in low-carbon steels, Al-killed steels, although

the effect probably applies to other steels as well. Figure 2 demonstrates this effect in low carbon 0.04%C
Al-killed steel, where bake hardening represents the increase in yield strength for a tensile specimen
strained 2 percent and heated for 20 minutes at 170C.
Hanai et al. attributed the increase in bake hardening by phosphorus to grain refinement during annealing.
The steel with 0.06%P exhibited a ferrite grain size one order of magnitude finer than similar steel with
0.01%P given similar processing treatments. Furthermore, phosphorus had a negligible effect on the
solute carbon a nitrogen contents remaining in solution after processing. Therefore, grain refinement by
phosphorus was cited as the cause of increased bake hardening.

Figure 2: Effect of phosphorus content on the bake hardening increment in 0.04 Al-killed steels
(1kg/mm2 = 9.8 MPa)

Ductility
As expected, the strengthening effect of phosphorus is accompanied by a concomitant decrease in
ductility. For example, Figure 3 shows the relationship between the decrease in elongation and increase in
tensile strength resulting from P, Mn and Si additions to a Ti-stabilized, ULC steel. Thus, phosphorus
(and other strengthening elements) decreases formability so that a balance between strength and
formability must be considered in designing high strength formable steels. At high phosphorus levels
(depending on composition, processing, etc.) ductility is severely limited by embrittlement phenomena
associated with phosphorus segregation to grain boundaries.

Figure 3: Decrease in ductility (percent total elongation) with tensile strength for P, Si and Mnstrengthened Ti-stabilized, ultra low carbon steels

Effect of Phosphorus on the Properties of Carbon

Steels: Part Two
Abstract: This article describes effect of phosphorus on the texture and drawability (R value), spot
weldability, magnetic properties and coating properties of carbon steels.

Texture (R-Value)
Anisotropy of plastic-flow properties has a strong influence on the deep drawability of sheet steels. For
good drawability the through-thickness strength in order to avoid thinning during drawing operations. A
useful measure of drawability is the R-value, defined as the ratio of width to thickness strain in a uniaxial
tensile specimen at fixed extension (typically 17 percent). Since the R-value generally varies with
direction in the sheet, a mean R-value is typically reported. A high R-value implies good drawability with
values of 2.0 being considered excellent.
Plastic anisotropy is determined by crystallographic texture i.e. the orientation distribution of grains
within the sheet, which is closely related to steel composition and processing. In body centered cubic
materials (e.g. carbon steels) favorable drawing textures correspond to a high proportion of {1 1 1} planes
aligned parallel to the sheet surface. The topic of annealing textures in steels has been thoroughly
reviewed by Hutchinson.
Phosphorus affects the texture and R-value of cold rolled steel in a complex manner that is dependent on
the composition of the steel and the annealing treatment. Early investigations showed that up to 0.04
percent of phosphorus markedly improves the R-value of low-carbon rimmed steel given a decarburizing
open-coil anneal. Hu also noted an improvement in the R-value from about 1,5 to 2,0 with the phosphorus
content ranging from %P=0,0040,12 in vacuum-melted rimmed steels given a simulated batch anneal.

However, Al-killed steels that were air melted showed a less dramatic improvements in the R-value which
appeared to reach a maximum at about %P=0.08. Hu proposed that segregation of phosphorus to grain
boundaries and subgrain boundaries influences the nucleation and growth of recrystallized grains. He
showed that the recrystallized texture is significantly altered by phosphorus additions to Al-killed steel.
More recent work has demonstrated the importance of the heating rate during annealing, carbide
morphology and solute carbon content. Ono et al. showed that both low phosphorus (%P=0.016) cold
rolled, low carbon, Al-killed steels exhibit a maximum in R value versus heating rate during annealing. At
an optimum heating rate of about 50C/hour, the high phosphorus steel had a lower R value than the low
phosphorus steel, whereas the opposite was observed at heating rates greater than 80C/hour. These
effects were attributed to an interaction between P and AlN precipitation during annealing, which in turn,
affected the final grain structure and crystallographic texture.
In a subsequent paper, these authors describe an experiment whereby interference from AlN was
eliminated by heat treatment prior to cold rolling. Treatments were varied such that a decarburized steel
(20-30 ppm C) and steels with fine and coarse Fe-carbide precipitates were produced. Figure 1
summarizes the results of annealing experiments for these steels.

Figure 1: Effect of the heating rate on the R-value as a function of the phosphorus content and carbide
morphology in Al-killed steels. ALN precipitation was complete prior to cold rolling and annealing.

For the decarburized steel, the R-value decreased with both increasing P content and faster heating rate
during annealing. This apparently reflects the behavior of ultra-low-carbon, carbide-free matrix. At low
heating rates phosphorus improved the R-value for both coarse- and fine-carbide steels. This may indicate
that phosphorus reduces the inhibiting effect of carbon which enters solution via carbide dissolution prior
to recrystallization. At high heating rates phosphorus degraded the R-value of coarse-carbide steel. In the
fine-carbide steel, the R-value first increased slightly and then decreased with increasing P content. This
suggests that either phosphorus had insufficient time to segregate to grain or subgrain boundaries or that
carbide dissolution had not progressed sufficiently to show a beneficial effect of phosphorus.
Hutchinson concluded that phosphorus is only beneficial in those situations where dissolved carbon
would otherwise degrade texture. Furthermore, in order to be effective, phosphorus must be allowed to
segregate e.g. during slow heating. However, in the case of Ti stabilized, ULC steels where virtually
carbon does not exist in solution during annealing, small phosphorus additions tend to improve the Rvalue. Figure 2 shows this effect as a function of grain size for samples rapidly heated to 800C. Note that
at the same time grain size, the R-value of the P-bearing steel is up to 0.3 units greater than that of the
base steel. Further study is needed to elucidate the effect of phosphorus on texture development in
stabilized steels.

Figure 2: R-value as a function of grain size for rapidly annealed, Ti-stabilized, ultra-low carbon steels
containing Si, Mn or P.
Although the available data is somewhat confusing, up to 0.1 percent of phosphorus does not appear to
seriously impair the drawability (R-value) of carbon steels. Furthermore, with the proper choice of
processing parameters, drawability can be significantly improved by additions of phosphorus; any
improvement is usually a side benefit to the strengthening effect of phosphorus, however. It is interesting
to note that phosphorus is the only known element capable of increasing both the strength and R-value of
steel.

Spot Weldability
Sawhill and Baker compared the resistance spot-welding characteristics of plain-carbon steel with those
of rephosphorized steel containing 0.04 percent to 0.12 percent of phosphorus. Adequate weld button size,
strength and toughness were obtained over a practical range of welding conditions.

To obtain an adequate button size over a large range of weld currents, electrodeface diameters and
welding times need to be increased slightly compared with those of plain-carbon steels. Others report
excellent weldability of rephosphorized Al-killed steel and galvannealed Ti stabilized, ULC steel,
although it has been suggested that the phosphorus content be limited to approximately 0.1 percent.

Magnetic Properties (Core Loss)

Phosphorus is added in amounts up to 0.15 percent to cold rolled, motor-lamination steels in order to
reduce AC core loss during service. A significant portion of core loss is due to eddy currents, and this
contribution depends inversely on electrical resistivity. Phosphorus is desirable for this purpose because it
strongly increases resistivity at low cost. The enhanced punchability of motor laminations due to the
hardening effect of P is an additional benefit gained by adding phosphorus to these steels.

Coating Behavior
Phosphorus has a strong effect on the alloying rate of galvannealed Fe-Zn coatings in low-carbon,
aluminum killed steels. Phosphorus in the base steel retards alloy layer formation, thus reducing the
alloying rate during galvannealing. This is not necessarly detrimental since the galvanneling temperature
can be increased to maintain high productivity.
However, very soft steels may encounter shapes problems at galvanneling high temperatures.
Nevertheless, tight control of phosphorus is desirable in order to specify optimum operating conditions
(temperature, line speed, etc.) for a given steel grade. Variable phosphorus content can lead to difficulties
in process control.
Phosphorus exerts a beneficial effect on the galvanneling reaction by inhibiting the so called "outburst
reaction" at grain boundaries which contributes to poor powdering performance. The outburst reaction
refers to the formation of brittle Fe-Zn intermetallic compound at ferrite grain boundaries. Volume
expansion during this process causes the grain boundary to open up, breaking a protective Fe-Al layer.
This allows liquid Zn to locally form new intermetalics. Phosphorus segregation to grain boundaries
apparently inhibits the local Fe-Zn intermetallic formation.
Figure 3 shows results of investigation the effects of phosphorus in steels on the formation of Fe-Zn
compounds in continuously galvanized Nb-B-P-ultra low carbon steel sheets (%C=0.006; %Mn=0.27;
%P=0.076; %S=0.005; %Nb=0.016; %B=0.0018; %Alsol=0.004; %N=0.0023) which suggest that
phosphorus inhibits the formation of outburst structure.

Figure 3: The effects of phosphorus on formation of Fe-Zn compounds outburst structure.

Sheet steels coated with Zn or Al-Zn can become embrittled by heating in the temperature range of 335C
to 400C. This is a result of Zn penetration into the grain boundaries at temperatures less than the melting
point of Zn. Embrittlement can be prevented if the P content in the steel exceeds 0.04 percent.

Phosphorus segregation to ferrite grain boundaries inhibits intergranular diffusion of Zn, thus preventing
Zn embrittlement.
Phosphatability was found to be markedly improved by the addition of 0.07 percent P to a Nb-bearing,
ULC steel. In addition, phosphorus markedly improved the corrosion resistance of phosphated steel. The
addition of phosphorus to certain enameling steel grades has been reported to enhance fishscaling
resistance and after-fire strength. Furthermore, phosphorus accelerates etching and nickel deposition rates
during pre-enameling treatments. Although these latter effects may be advantageous, process control
difficulties can arise if the phosphorus content is not consistently controlled to a predetermined level.

Boron in Steel: Part One

Abstract: At the atmospheric pressure and temperature of 0C boron is a solid material. Boron optimum
quantity which has to be added in the steel to achieve maximum hardenability, based on experience is
about 0.0003 to 0.0030% B.
Boron is supplied to steelmakers as ferroboron or as one of several proprietary alloys. Choice of addition
depends, as always, on steelmaking practice, product mix and volume, individual operators` experience
and preference, and price.

The Basic Properties of Boron

The name "boron" originates from the Armenian-Persian linguistic area: buraq or burah for borax, one of
the most widely-known boron compounds, namely sodium sodium tetraboratedecahydrate. As long ago as
the Middle Ages borax was exported under the name "Tincal" from the salt lakes of Central Asia to
Europe, where it was used as an aid in soldering and melting.
The proportion of boron in the earths outer crust is estimated to be to 10ppm and in nature boron does
not occur in the elementary state, but always combined with oxygen. The technically most important
boron-containing minerals are:

Borax (Tincal): Na2O x 2B2O3 x 10H2O;

Tincalconite: Na2O x 2B2O3 x 5H2O;
Kernite (Rasorite): Na2O x 2B2O3 x 4H2O;
Boracite: 5MgO x MgCl2 x 7B2O3;
Colemanite: 2CaO x 3B2O3 x 5H2O;
Sassolin: B2O3 x 3H2O.

The greatest deposits of boron are located in Kazakhstan, California, Argentina and Turkey. Boron was
first successfully produced in 1808 by H. Davy, as amorphous. Boron is the only nonmetal of the third
main group of the periodic table. At the atmospheric pressure and temperature of 0C boron is a solid
material. It has six isotopes, some of which are radioactive with very short time of semi decay, below 1
second. Some of the most important properties of boron are listed in the tables 1, 2 and 3.
Table 1: Boron: structural data
Modification
Amorphous
Color

Brown

Phase

Temperature of occurrence, C

800-1100

Lattice type

Crystaline
Black-grey

1300

rhombohedral
a=1,789 nm
b=0,895 nm
c=1,015 nm

1100-1300
tetragonal

Table 2: Boron: mechanical properties

Amorphous
Crystaline
mod. 2.46
mod. 2.35
mod. 2.37

Density, g/cm

1.73

Hardness

9.3

Tensile strength, MPa

amorphous 1.6-2.4
fibres 2.6-3.1

Compressive strength, MPa

0.5

Elasticity modul, MPa

440
Table 3: Boron: thermodynamic data
Flame point, C
70
Melting point, C

2300

Boiling point, C

2550

Coefficient of thermal expansion 20-750

1.1- 8.3 nm/m.k

Latent heat of vaporization

34900 kg/kg

Latent heat of fusion

22000 kJ/kg

Latent heat of combustion

5.4 kJ/kg

Diffusion coefficient in -Fe

D= 0.002 e-21000RT
for t=1000 C : D=0.002

According to P.E. Brushby et al. boron diffusion velocity is the same as carbon diffusion velocity
(diffusion coefficient D=0,002e-21000/RT). With carbon content of up to 0.43%, the solubility of boron in the
austenite lattice is independent of the carbon content. Carbon diffusion is not affected up to boron
contents of 0,009%.

Boron Solubility in Pure Iron

There are different opinions about the positions of boron atoms in the iron crystal lattice. Based on
comparison of the diffusion coefficients of carbon and boron, Jandeska and I.J.Morral have concluded
that the boron atoms are interstitially dissolved in the -Fe lattice. C.C. McBride, J.W. Spretnak,
R.Speiser have reached the same results based on comparison of the theoretical consideration of the boron
atoms radius and interatomic distances in the -Fe lattice. However, these geometric considerations ignore
the mechanisms of physical and chemical bonding.
R.M.Goldhoff and J.W.Spretnak found by X-ray deflection measurements that the lattice parameter in
gamma iron is reduced in the presence of boron. They took this as a proof of a substitutional dissolution
of the boron atoms in the austenite lattice. Due to the atomic radii of boron and iron, they considered the
position of the boron atoms at the lattice locations to be more favorable than at intermediate lattice
locations.
They also discovered that the difference between the lattice parameters of pure iron and boron-containing
iron decreases with increasing temperature. From this they concluded that with increasing temperature
more boron atoms migrate from the lattice to the grain boundaries, where boron separations have actually
been found. However, these authors did not exclude the possibility that a smaller number of boron atoms
may also occupy intermediate lattice locations.
There is several different works on the Fe-B binary system. Figure 1 shows a diagram prepared by
O.Kubaschevsky. It shows two eutectics, one at 17 atomic percent of boron, the other at 63.5% of boron.

Figure 1: Kubaschewsky Fe-B phase diagram

Within the range between these two eutectics, the liquidus temperature varies between 1149C, the
eutectic temperature at 17 atomic percent of boron, and 1590C for the alloy with 50 atomic percent of
boron. Accordingly, the melting temperature of iron can be lowered by more than 150C to the maximum
of 350C (at 17 atomic percent of boron) by the adding of 5 to 30 atomic percent of bor. By increasing
proportion of boron in the ferroboron from the second eutectic, the liquidus temperature rises steadily and
almost linearly up to the melting temperature of pure boron. Accordingly, in the above diagram, iron
boride (FeB) has 16.23 weight percent of boron, a rhombic lattice and extreme hardness of 2300 HV0.2
Iron-II-boride (Fe2B) has 8.83 weight percent of boron, a tetragonal lattice and hardness of 1800 to 2000
HV0.2 (preferable as long as FeB is being avoided). Many authors have made more precise investigations
of the iron/boron binary system in the iron rich corner. According to Houndremon's binary phase diagram
Fe-B (Figure 2), in the low concentration region of boron the maximum solubility of boron is 0,021% at
1149C. In the meantime, with the temperature decrease its solubility decreases too, as far as down to
0.0021% at 906C.
At the same time this temperature is perytectoide for perytectoide reaction at 0.0082%B. Boron solubility
in -Fe suddenly decreases and at 710C only about 0.0004% of boron substitionally dissolved.

Figure 2: Equilibrium phase Fe-B diagram for low boron concentrations

J.W.Spretnak investigated whether it is possible for boron to form a film surrounding austenitic grain in
the steel and concluded on the basis of the geometrical considerations that it is impossible. Instead, they
discovered a point Fe2B precipitation at the grain boundaries. In the steel, boron can be dispersed in
matrix in the form of Fe2B, boride with size of 20 to 30x10-8 cm and free, which segregates predominantly
surrounding primary austenite grain boundaries. This small amount of the soluble boron arranged along
grain boundaries, evidently retards - transformations by diffusion, namely it prevents feritic reaction
thus enhancing hardenability of the steel.
Boron optimum quantity which has to be added in the steel to achieve maximum hardenability, based on
experience is about 0.0003 to 0.0030% B. Boron addition beyond the mentioned values deteriorates
hardenability because the excess of boron atoms precipitates as the surface centered cube Fe23(CB)6
borocarbide which can be a ferrite nucleation preferential place.

Available Forms
Boron is supplied to steelmakers as ferroboron or as one of several proprietary alloys. Choice of addition
depends, as always, on steelmaking practice, product mix and volume, individual operators' experience
and preference, and price. A steelmaker should choose that addition agent giving the highest and most
reliable recovery consistent with his overall melt shop economics.
Ferroboron is the lowest cost addition agent. Boron content is relatively high: standard grades are sold
with incremental boron levels between 12 and 24% B. Major impurities are carbon (0.10-1.5%), silicon
(0.30-4.0%) and aluminum (0.5-8.0%). A typical analysis will include 18.0% B, 0.50% C, 0.50% Si, 0.2%
Al, 0.03% P, and 0.01% S. All except boron are maximum values. Product is supplied in lump form, 2 in.
or 1 in. x down, packaged in 250 kg or 500 lb steel drums, or supersacks (bulk bags) of up to 3000 lb
(1360 kg) capacity. Many customers apply a minimum size limit, such as 5 mm (0.2 in.), in order to
minimize the amount of fine material, which can give poor recoveries in less well-controlled melting
practices. Ferroboron is also available as cored wire.

Because ferroboron does not contain appreciable concentrations of protective elements, it requires greater
care than the proprietary alloys in order to give adequate and consistent results. It is normally added after
other oxygen/nitrogen scavengers, such as ferrotitanium.
The proprietary boron addition agents are more expensive than ferroboron on an initial cost basis but are
often preferred for their greater efficiency, ease of application and more consistent results. All will contain
varying proportions of oxygen and/or nitrogen scavengers such as titanium, aluminum, silicon and
zirconium. These elements generally have an even greater affinity for oxygen and nitrogen than boron.
The most common proprietary addition agent typically contains 2.0% B, 15% Al, 30% Ti, 10% Si, bal.
Fe. This product's high scavenger/boron ratio ensures its effectiveness for all boron steels, provided they
have been adequately deoxidized first.
A variety of other composition proprietary boron addition alloys are available, with boron contents
varying between 0.5% and 4%. Generally, the higher the ratio of boron to scavenger elements, the greater
the care required to ensure adequate recovery of the boron in the steel.
Proprietary boron addition agents are sold in lump form 1-1/4 in. and 2 in. x down, packaged in bags,
cans or large drums.

Boron in Steel: Part Two

Abstract: Boron is useful as an alloying element in many materials, but in this paper it will be illustrated
as an alloying element in the steel because of its effect on hardenability enhancement. Boron is added to
unalloyed and low alloyed steels to enhance the hardness level through enhancement hardenability. Boron
added to high-speed-cut steels, for example, containing 18%W, 4%Cr and 1%V, enhances their cutting
performance, but reduces their forging qualities.

Boron in steel as an alloying element

Boron is useful as an alloying element in many materials, but here it will be illustrated as an alloying
element in the steel because of its effect on hardenability enhancement. Boron is added to unalloyed and
low alloyed steels to enhance the hardness level through enhancement hardenability. Boron added to highspeed-cut steels, for example, containing 18%W, 4%Cr and 1%V, enhances their cutting performance,
but reduces their forging qualities.
Addition of boron in a quantity of up to 0.01% to austenitic steels also improves their high-temperature
strength. Boron steels are used as high-quality, heat-treatable constructional steels, steels for carburization
and cold forming steels such as steels for screws. The addition of 5 to 50 ppm B to ferritic steels
containing 14 to 18% Cr may improve the surface quality of stainless strips by avoiding errors, such as
scale, ribbing a roping, and ridging, which otherwise frequently occur in strip production.
The basic effect of boron on in the steel is the enhancement of hardenability, which is evident already at a
very small concentration, of the degree of 0.0010% of boron. It is added to unalloyed and low alloyed
steels for the hardness level enhancement through the hardenability. Even in the small quantity of the
degree of size up to 100 ppm, boron gives the same effect of the hardenability enhancement as other more
expensive elements which must be added in much bigger quantity. For example the addition of 30 ppm B
in SAE replaces approximately 1%Ni, 0,5%C, 0,2%Mn, 0,12%V, 0,3%Mo or 0,4%Cr.
The Figure 1 shows hardenability curves of the boron low alloyed steels (13MnCrB5) compared to the
steel without boron (16MnCr5).
An addition of 30 ppm of boron in steel which contains approximately 0.15%C, 1%Mn and 0.9%Cr
shows a clear increase in hardness of almost 50% to a larger depth from the surface than in the case of a
steel of identical composition, but free from boron (see Figure 1). According the same authors, there is no

difference in hardness on the surface between the boron-containing and the boron-free steel, which can be
seen in the Figure 1, too. Accordingly, the incipient hardness is therefore determined not by boron, but by
the martensitic structural state influenced by the carbon content. The hardness-enhancing effect of boron
comes into play only below the surface.
The mechanism which is decisive for the enhancement of hardenability by boron is a delay in the
transformation to the bainite, ferrite and pearlite structures, which are softer than martensite. Unless
prevented by boron, these softer structures would be formed during the cooling from the austenitisation
temperature, after annealing or hot working.

Figure 1: Boron effected hardenability of steel

The Boron hardenability effect

An outstanding feature of boron steels is the improvement in hardenability produced by the addition of
even a minute quantity of boron. It is generally accepted that a hardenability peak is reached when the
quantity of boron is between 3 and 15 ppm. In an excessive amount of boron (>30 ppm) is present, the
boron constituents become segregated in the austenite grain boundaries, which not only lowers
hardenability, but also may decrease toughness, cause embrittlement and produce hot shortness. The
affect of boron on hardenability also depends on the amount of carbon in the steel. The effect of boron
increases in inverse proportion to the percentage of carbon present.
Boron must be in its atomic state to improve hardenability, which means that care must be taken during
steel production for the boron to be effective. Boron may also become ineffective if its state is changed by
incorrect heat treatment. For example, high austenitizing temperatures must be avoided as well as
temperature ranges where certain boron precipitates occur.
Hardenability is highly dependent on the behavior of oxygen, carbon and nitrogen present in steel. Boron
reacts with oxygen to form boron oxide (B2O3); with carbon to form iron boroncementite (Fe3(CB)) and
iron boroncarbide (Fe23(CB)6); and with nitrogen to form boron nitride (BN). Loss of boron by oxygen is
presented by making the boron addition to silicon-aluminum killed steels and by using good ladle and
mold practices. Strong nitride formers (titanium, aluminum, and zirconium) protect the boron from
reaction with nitrogen. For example, if nitrogen is fixed by using titanium, satisfactory hardenability is
obtained in the temperature range up to 1830F (1000C) provided that the steel contains about 5-20 ppm
of boron.

The hardenability of boron steel is also closely related to austenitizing conditions and is generally said to
decrease by heating above 1830F (1000C). Boron steel must also be tempered at a lower temperature
than other alloy element steels of the same hardenability.

Applications
Boron steels are used for a variety of applications, as a wear material and as a high strength structural
steel. Examples include punching tools, spades, and knives, saw blades, safety beams in vehicles etc.
Carbon-manganese-boron steels are generally specified as replacements for alloy steels for reasons of
cost: C-Mn-B steels are far less expensive than alloy steels of equivalent hardenability. Applications for
these steels include earth scraper segments, track links, rollers, drive sprockets, axle components and
crankshafts.
Boron alloy steels are specified when the base composition meets mechanical property requirements
(toughness, wear resistance, etc.), but hardenability is insufficient for the intended section size. Rather
than call for a more highly alloyed and therefore more expensive steel, a user may simply specify the
corresponding boron grade, thereby ensuring suitable hardenability.
An expanding area of boron usage is the field of high strength low alloy (HSLA) and other structural
steels. These may be supplied as hot rolled or as quenched and tempered (for boron grades, the latter are
more common). Boron assures adequate hardenability in heavier plate sections.
Boron is sometimes used in non-heat treated steels. Ferroboron may be added as an intentional nitrogen
scavenger in carbon steels for automotive strip stock. By avoiding interstitial nitrogen, boron makes the
steel more formable. Aluminum is sometimes used for a similar duty, but AlN is slower to precipitate, so
requiring higher annealing temperatures. Boron addition makes the steel more formable and eliminates
the need for strain age suppressing anneals.
Boron has a high neutron absorption capability. For this reason, it is added to certain types of stainless
steel for use in the nuclear industry. Levels of 4% boron or more have been used, but the lack of hot
ductility and weldability mean that boron contents of 0.5 to 1.0% are more common for neutron
absorption application. Nonetheless, even at these boron contents, the ferroboron has to be of the highest
purity.
This range of medium carbon steels with a deliberate boron addition improves hardness during heat
treatment (Boron 922, C=0.25-0.30% and Boron 921, C=0.38-0.42%). Toughened by tempering
following oil or water quenching, boron steels possess a hardness equivalent to that of much higher
carbon steels and of more expensive low alloy steels. Advantages of boron steels are; improved cold
formability, lower delivered hardness giving improved blanking tool life, improved weldability due to low
carbon equivalents, lower tempering temperatures giving savings on energy, and good case hardening
response. Typical applications include toecaps and chains.
The type of boron steel used on vehicles today has extremely high strength. The boron steel used on
Volvo cars has a yield point of about 1,350-1,400 MPa (196,000-203,000 psi). Thats about four times
stronger than average high-strength steel. But the process used to make it that strong takes away some of
the steels workability properties, such as being able to straighten it.
For now, boron steel is found primarily on European vehicles, such as the dash panel on the 2002 Porsche
Cayenne SUV, the safety bar around the rear seats on the 2003 Porsche Boxster, the door guard beams on
the 2003 Porsche 911 Carrera, and the inner B-pillars on the 2003 Mercedes-Benz E Class. Volvo
probably uses boron steel the most. Boron is used on the bumper reinforcements and guard beams on the
2004 Volvo S40 sedan and 2005 V50 station wagon. The 2003 Volvo XC90 SUV has several applications
of boron steel, including the inner B-pillar reinforcements, the roof bow between the B-pillars (if there is
no sunroof), and the inner rear body panels. The 1999-2004 S80 and 2001-2004 V70 and S60 also have
boron steel inner and outer rear body panels.

Steel Deoxidation: Part One

Abstract: Deoxidation is the removal of excess oxygen from molten metal. The procedure involves
adding materials with a high affinity for oxygen, the oxides of which are either gaseous or readily form
slags. The deoxidation of steel is usually performed by adding Mn, Si and Al, or rarely by adding Cr, V,
Ti, Zr and B.
The deoxidation of molten steel exhibits a paradox. By increasing the concentration of deoxidizer in the
melt over some critical value reoxidation of steel takes place. A few examples of the reoxidation of steel
by adding the usual deoxidizers (Si and Al) are examined in this article.
Deoxidation is the removal of excess oxygen from molten metal. The procedure involves adding materials
with a high affinity for oxygen, the oxides of which are either gaseous or readily form slags. The
deoxidation of steel is usually performed by adding Mn, Si and Al, or rarely by adding Cr, V, Ti, Zr and
B.
The deoxidation of molten steel shows a paradox. By increasing the concentration of deoxidizer in the
melt over some critical value reoxidation of steel takes place. A few examples of the reoxidation of steel
by adding the usual deoxidizers (Si and Al) are examined in this article.
Deoxidation is the last stage in steelmaking. In the Basic Oxygen Furnace (BOF) and other similar
steelmaking practices the steel bath as the time of tapping contains 400 to 800 ppm activity of oxygen.
Deoxidation is carried out during tapping by adding into the tap-ladle appropriate amounts of
ferromanganese, ferrosilicon and/or aluminum or other special deoxidizers. If at the end of the blow the
carbon content of the steel is below specifications, the metal is also recarburized in the ladle. However,
large additions in the ladle are undesirable, because of the adverse effect on the temperature of the metal.
Eight typical conditions of commercial ingots, cast in identical bottle-top molds, in relation to the degree
of suppression of gas evolution are shown schematically in Figure 1. The dotted line indicates the height
to which the steel originally was poured in each ingot mold. Depending on the carbon content and
particularly of the oxygen content, the ingot structures range from that of a fully killed or dead-killed
ingot N1 to that of a violently rimmed ingot N8. Included in the series are indicated in figure 1 i.e.
killed steel N1, semikilled steel N2, capped steel N5, and rimmed steel N7.

Figure 1: Series of typical ingot structures

Rimmed steel usually is tapped without having made additions of deoxidizers to the steel in the furnace
or only small additions to the molten steel in ladle, in order to have sufficient oxygen present to give the
desired gas evolution by reacting in the mold with carbon. The exact procedures followed depend upon
whether the steel has a carbon content in the higher ranges i.e. %C=0.12-0.15 or in the lower ranges, e.g.
%C=max 0.10 .When the metal in the ingot mold begins to solidify, there is a brisk evolution of carbon
monoxide, resulting in an outer ingot skin of relatively clean metal low in carbon and other solutes. Such
ingots are best suited for the manufacture of steel sheets.

Capped steel practice is a variation of rimmed steel practice. The rimming action is allowed to begin
normally, but is then terminated after a minute or more by sealing the mold with a cast-iron cap. In steels
with a carbon content greater than 0.15% the capped ingot practice is usually applied to sheet, strip, wire
and bars.
Semikilled steel is deoxidized less than killed steel and there is enough oxygen present in the molten steel
to react with carbon forming sufficient carbon monoxide to counterbalance the solidification shrinkage.
The steel generally has a carbon content within the range %C=0.15-0.30 and finds wide application in
structural shapes.
Killed steel is deoxidized to such an extent that there is no gas evolution during solidification. Aluminum
is used for deoxidation, together with ferro-alloys of manganese and silicon; in certain cases calcium
silicide or other special strong deoxidizers are used. In order to minimize piping, almost all killed steels
are cast in hot-topped big-end up molds.
Killed steels are generally used when a homogeneous structure is required in the finished steels. Alloy
steels, forging steels and steels for carburizing are of this type, when the essential quality is soundness. In
producing certain extra-deep-drawing steels, a low-carbon (%C=max 0.12) steel is killed, usually with a
substantial amount of aluminum that is added in the ladle, in the mold or both.
Although the deoxidation of steel by aluminum suppresses the formation of carbon monoxide during
solidification, and hence suppresses blow holes, there are many steel processing operations where
aluminum killing of steel is undesirable. For example, it is widely recognized that certain alloy steels to
be cast as large ingots should not be subject to aluminum killing, because of the piping and of deleterious
effects of alumina inclusions on the subsequent processing of ingots for certain applications, e.g.
generator-rotor shafts.
It has been recognized from the early days of the continuous-casting operation nearly two decades ago
that casting difficulties and poor surface conditions are often experienced with aluminum-killed steels. It
is for these reasons that other forms of deoxidation are often preferred in a number of steel-processing
operations, e.g. silico-managanese deoxidation and/or vacuum carbon deoxidation.

Deoxidation equilibria
Deoxidation reactions can be described using the deoxidation equilibrium constant. A wide spectrum of
deoxidation equilibria pertaining to the most common deoxidants for steel is summarized in Table 1 as a
log-log plot of the concentration of oxygen in solution in liquid steel against that of the added elements.
Table 1: Solubility of the products of deoxidation in liquid iron.
Equilibrium constant K* Composition range K at 1600C
log K
[aAl]2[aO]4

< 1 ppm Al

1.1 x 10-15 -71600/T + 23.28

[aAl]2[aO]3

< 1 ppm Al

4.3 x 10-14 -62780/T + 20.17

[aB]2[aO]3
[aC] [aO]3

> 0.02% C

[aCr]2[aO]3

> 3% Cr

1.1 x 10-4 -40740/T + 17.78

[aMn] [aO]

> 1% Mn

5.1 x 10-2

[aSi] [aO]

1.3 x 10-8

2.0 x 10-3

-5

-1168/T - 2.07
-14450/T + 6.43

> 20 ppm Si

2.2 x 10

-30410/T + 11.59

[aTi] [aO]2

< 0.3% Ti

2.8 x 10-6

[aTi] [aO]

> 5% Ti

1.9 x 10-3

[aV]2[aO]4

< 0.10 V

8.9 x 10-8 -48060/T + 18.61

[aV]2[aO]3
> 0.3% V
2.9 x 10-6 -43200/T + 17.52
Activities are chosen such that aMn %Mn and aO %O when %MO
Square brackets [ ] denote component present in molten steel

Temperature (T) is on the Kelvin scale.

In all cases, the oxygen and the alloying element in solution are in equilibrium with the appropriate gas,
liquid or solid oxide phases at 1600C, e.g. 1 atm CO, pure B2O3, pure Al2O3 etc. The curves for Mn, Si
and C are from compiled data. The curves for Cr, V, B, Ti and Al are based on the recent work done in
this laboratory by Fruehan using the oxygen galvanic cell previously described in measuring the
equilibrium oxygen potentials.
Deoxidation reactions can be described using the deoxidation equilibrium constant. The reaction when the
alloying element (M) is added to the steel can be represented by:
MxOy = xM + Yo .....(1)
The deoxidation constant assuming pure MxOy forms (i.e. unit activity for MxOy) is given by:
K = (hM)x(hO)y .....(2)
Where hM and hO are the Henrian activities defined such that activity of the components is equal to its
weight percent at infinite dilution in iron.
Hi = fi(wt.% i) .....(3)
The activity coefficient fi can be corrected for alloying elements by use of the interaction parameter eji
(d log fi/d log wt%j) = eji .....(4)
Table 2 shows the coefficients of interaction for the common elements of carbon and stainless steels at
1600C.
Table 2: The coefficients of interaction for the common elements of carbon and stainless steels at 1600C
Metal
Al C Mn P
S
Si
Ti H N O Cr Ni
%i

0.05 0.45 0.02 0.01

Carbon steel 1600C fi 1.05 1.06 1.0

1.1

1.0

0.3

0.05

1.15 0.93 1.0 0.97 0.85

ai

0.053 0.45 0.022 0.01 0.345 0.046

%i

0.05 0.45 0.02 0.01

0.3

Stainless steel 1600C fi 3.6 0.49 1.0 0.32 0.66 1.24

ai

0.05

18

9.4 0.93 0.17 0.21 0.97 1.0

0.025 0.45 0.006 0.007 0.372 0.47

17.5 8.0

For most low alloy steels encountered in ladle metallurgy the activity coefficient can be taken as unity
and equation 2 reduces to:
KM = (%M)x(%O)y .....(5)
To illustrate how to use these constants consider a steel containing 0.1%Si at 1600C (2912F) in
equilibrium with SiO2. The value of KSi is given by:
KSi = (%Si)(%O)2 .....(6)
KSi = 2.2 x 10-5
Therefore:
(%O)2 = 2.2 x 10-4

(%O) 0.015 or 150 ppm.

It is important to remember that these calculations are for soluble oxygen content; the total oxygen
content which includes both the soluble oxygen and the oxygen associated with inclusions could be much
higher.
For single element deoxidation, the solubility of oxygen in liquid iron at 1600C (2912F) is given as a
function of the concentration of the alloying element. In each case, the melt is in equilibrium with the
respective pure oxide; e.g. SiO2, Al2O3 etc. It can be clearly seen that aluminum is the strongest of the
common deoxiders followed by titanium. Rare earths are about as strong aluminum as deoxidizers and
will be discussed later in detail.

Steel Deoxidation: Part Two

Abstract: Deoxidation is the removal of excess oxygen from molten metal. The procedure involves
adding materials with a high affinity for oxygen, the oxides of which are either gaseous or readily form
slags. The deoxidation of steel is usually performed by adding Mn, Si and Al, or rarely by adding Cr, V,
Ti, Zr and B.
The deoxidation of molten steel exhibits a paradox. By increasing the concentration of deoxidizer in the
melt over some critical value reoxidation of steel takes place. A few examples of the reoxidation of steel
by adding the usual deoxidizers (Si and Al) are examined in this article.
n all steelmaking processes, except for the acid silicon reducing process, the steel must be deoxidized
after having been brought to the specified carbon content to make the dissolved oxygen inactive and
prevent further oxidation of carbon.
There are primarily three elements used in steel deoxidation:

Manganese and silicon (as low and high carbon ferro alloy or as silicomanganese alloy) and
Aluminum, about 98% of purity.

Deoxidation with Fe-Mn

When the steel is partially deoxidized with Mn, the iron also participates in the reactions, forming liquid
or solid Mn (Fe)O as the deoxidation product.
[Mn] + [O] MnO
[Fe] + [O] FeO
The state of equilibrium of steel with the deoxidation product Mn(Fe)O is shown in Figure 1.

Figure 1: Manganese and oxygen contents of iron in equilibrium with FeO-MnO liquid or solid solution.

Deoxidation with Si-Mn

The deoxidation by silicon is much more complete than that by manganese and simultaneous deoxidation
by these two elements gives much lower residual oxygen in solution, because of reduced silica activity.
Depending on the concentration of Si and Mn added to steel in the tap ladle, the deoxidation product will
be either molten manganese silicate MnO SiO2 or solid silica SiO2.
[Si] + 2[O] SiO2
[Mn] + [O] MnO

(1)
(2)

One of the early pioneering studies of slag-metal reaction equilibria is that attributed to Korber and
Oelsen for their measurement of the equilibrium distribution of manganese and silicon between liquid
iron and MnO-FeO-SiO2 slag saturated with silica. The results of their experiments at 1600 10C are
shown in Figure 2.

Figure 2: Concentration of Mn, Si and O in liquid iron equilibrated with SiO2. Saturated manganese
silicate melts at 1600 10C.
Value of the equilibrium constant for Si deoxidation is already given in equation (1). The following
equilibrium relation is obtained for the Si-Mn deoxidation reaction.
KSi= aSiO2 / [%Si] [%O]2

(1a)

where the silica activity aSiO2 is with respect to solid SiO2 as the standard state.
The sum of the deoxidation reactions by silicon and manganese gives following equilibrium relation
[Si] + 2(MnO) = 2[Mn] + (SiO2)
KMnSi = {[%Mn]/aMnO}2 aSiO2/[%Si]
log KMn-Si = 1510/T + 1.27

(3)
(3a)

(3b)

where aSiO2 and aMnO are relative to pure solid oxides. For high concentration of silicon (Si>0.4%) the
activity coefficient fSi = 0.11 x [%Si].
The activities of MnO in manganese silicate melts have been measured by Rao and Gaskell. Their results
are in substantial agreement with the results of the earlier work by Abraham et all. The activity coefficient
of the oxides (relative to solid oxides) are plotted in Figure 3.

Figure 3: Activities in MnO-SiO2 melts with respect to solid oxides, derived from the experimental data.
For liquid steel containing Mn>0.4% the deoxidation product is a MnO-rich silicate with FeO<8%;
therefore the activity data in Figure 3 can be used together with equations (1) and (2) in computing the
equilibrium state of the Si/Mn deoxidation as given in Figure 4a. The deoxidation product being either
solid silica or molten manganese silicate depends on temperature, Si and Mn contents, as shown in Figure
4b.

Figure 4a and 4b: Equilibrium relations for deoxidation of steel with silicon and manganese at 1600C.

Deoxidation with Si/Mn/Al

Semi-killed steels with residual dissolved oxygen in the range 40 to 23 ppm are made by deoxidizing steel
in the tap ladle with the addition of a small amount of aluminium together with silicomanganese or a
combination of ferrosilicon and ferromanganese. In this case, the deoxidation product is molten
manganese aluminosilicate having a composition similar to 3MnO Al2O3 3SiO2. With small addition of
aluminum, e.g. about 35 kg for 220 to 240 t heat together with Si/Mn almost all the aluminum is
consumed in this combined deoxidation with Si and Mn. The residual dissolved aluminum in the steel
will be less than 10 ppm.

Figure 5: Al2O3 and SiO2 activities in MnO-Al2O3-SiO2 system for mass ratio of MnO/SiO2=1.
As is seen from Figure 5, for the deoxidation product MnO-Al2O3-SiO2 satured with Al2O3, the silica
activities are 0.27 at 1650C, 0.17 at 1550C and decreasing probably to about 0.12 at 1500C. Using
these activity data and equation (1) the deoxidation equilibria are calculated for Al/Si/Mn; these are
compared in Figure 6 with the residual oxygen [O] derived in ppm for the Si/Mn deoxidation at the same
concentration of Mn and Si.

Figure 6: Deoxidation equilibria with Si/Mn compared with Al/Si/Mn for the deoxidation product
saturated with Al2O3.

Deoxidation with Al
Aluminum is a very effective deoxidizer which is used in most steelmaking operations. Usually the
aluminum-deoxidation is carried out in ladle; in special cases the aluminum additions are also made in the
mold during ingot or continuous casting.
The equilibrium constants obtained from independent experimental studies agree with about a factor of
two. An average values for the equilibrium constant is given below,
Al2O3(s) = 2[Al] + 3[O]

(4)

K = [%Al]2 [ppm O x fO]3/aAl2O3

log K= -62 680 / T + 31.85

(4a)

(4b)

The alumina activity is with respect to pure solid Al2O3. The effect of aluminium on the activity
coefficient of oxygen dissolved in liquid steel is given by log fO= -3.9 x [%Al]. At low concentration of
aluminum, fAl = 1.0. Apparent equilibrium relations for the deoxidation products: pure Al2O3 and molten
calcium aluminate with %CaO/Al2O3= 1:1 are shown in Figure 7.

Figure 7: Deoxidation with aluminum in equilibrium with Al2O3 or molten calcium aluminate with
CaO/Al2O3 = 1:1
When the Al-killed steel is treated with Ca-Si the alumina inclusions are converted to molten calcium
aluminate. For the ratio %CaO/Al2O3 = 1:1 the activity of Al2O3 is 0.064 with respect to pure Al2O3 at
temperatures in the range 1500-1700C.

The Oxygen Steelmaking Process: Part One

Abstract: The oxygen steelmaking process is a generic name given to those processes in which gaseous
oxygen is used as the primary agent for autothermic generation of heat as a result of the oxidation of
dissolved impurities like carbon, silicon, manganese and phosphorus and to a limited extent the oxidation
of iron itself. Several types of oxygen steelmaking processes, like top blowing, bottom blowing and
combined blowing have been invented.
The oxygen steelmaking process is a generic name given to those processes in which gaseous oxygen is
used as the primary agent for autothermic generation of heat as a result of the oxidation of dissolved
impurities like carbon, silicon, manganese and phosphorus and to a limited extent the oxidation of iron
itself. Several types of oxygen steelmaking processes, like top blowing, bottom blowing and combined
blowing have been invented.
The essential features of conventional steelmaking are the partial oxidation of the carbon, silicon,
phosphorus and manganese present in pig iron and the accompanying reduction in the sulfur level. Blast
furnace hot metal for LD (Basic Oxygen Furnace) steelmaking process ideally contains about C=4.2%,
Si=max 0.8%, Mn=max 0.8%, S=max 0.05%, P=max 0.15% but these solute elements are diluted by the
addition scrap which forms some 20-30% of the metallic charge.

Refining Reactions
In LD basic oxygen steelmaking process, the oxygen required for the refining reactions is supplied as a
gas and both metal and slag are initially oxidized
O2(g) [O] .....(1)
Fe + [O] (FeO) .....(2)
2(FeO) + O2(g) (Fe2O3) .....(3)

Carbon
The actual distribution of oxygen between slag and metal is not easily determined since it is a function of
a number of variables including lance height and oxygen flow rate. The principal refining reactions is of
course the removal of carbon:
[C] + [O] CO2 .....(4)
[C] + (FeO) CO2 + Fe .....(5)
The Figure 1 represents an idealized diagram, showing the changes in concentrations of the elements in
LD metal bath during oxygen blowing. The basic thermodynamic data for these reactions are well
established and the equilibrium carbon and oxygen contents may be readily calculated for all the
temperatures and pressures encountered in steelmaking.

Figure 1: The changes of bath composition during the blow in a basic oxygen steelmaking converter
(idealized)
Oxidation of carbon during the oxygen converter process is most important, since the reaction increases
the temperature and evolves a large amount of gases CO and CO2 that cause agitation of metal and slag
and remove hydrogen, nitrogen and part of non-metallic inclusions from the metal. Owing to the pressure
of the oxygen supplied and the evolution of large quantities of gases, the liquid bath becomes an intimate
mixture of slag, metal and gas bubbles, with an enormous contact surface. Because of this, the reaction of
carbon oxidation is self-accelerated and attains a very high rate.

Silicon
In accordance with thermodynamic predictions, the removal silicon is usually completed relatively early
in the blow. The reaction may be represented by equations (6) and (7).
[Si] + 2[O] (SiO2) .....(6)
[Si] + 2(FeO) (SiO2) + 2Fe .....(7)

Manganese
Similar equations can be applied to manganese removal
[Mn] + [O] (MnO) .....(8)
[Mn] + (FeO) (MnO) + Fe .....(9)
Initially, the bath manganese level falls as a result of oxidation, but later, a slightly reversion, followed by
a second fall occurs. These changes in the manganese content of the bath are attributed to the combined
effects of rising temperature and variable slag composition, on the activities of manganese and ferrous
oxides, suggesting that the reaction is close equilibrium. This view is supported by the observation that at
the end of blowing, the manganese content was found to be 82% of the equilibrium value when lump lime
was used and 85% of the equilibrium value when powdered lime is injected.
In the middle part of blow, the (FeO) level in the slag falls as a consequence of the decarburization
process and the dilution that accompanies lime fluxing. However, towards the end of the blow, the (FeO)
increases again, as carbon removal becomes less intense and dilution begins to affect the activity of
manganese oxide with the result that manganese transfers from bath to slag. To some extent the
manganese loss may be minimized by rising the temperature.

Phosphorus
The partitioning of phosphorus between the slag and metal is known to be very sensitive to process
conditions and so far it has been possible to build a kinetic model based on simple assumptions.
The distribution of phosphorus between slag and metal has been reviewed by Healy, who concluded that
the thermodynamic behavior of phosphorus is best explained by a modified version of the ionic theory
first proposed by Flood and Grjotheim. The slag-metal reactions is written in ionic form in equation (10)
2[P] + 5[O] + 3 (O2-) 2(PO3-)4 .....(10)
Healy has expressed the equilibrium distribution of phosphorus by equations that apply to specific
concentration ranges in the CaO-SiO2-FeO system, i.e.:
log (%P)/[P] = 22 350/T + 7 log%CaO + 2.5 log Fet 24.0 .....(11)
log (%P)/[P] = 22 350/T + 0.08 log%CaO + 2.5 log Fet 16.0 .....(12)
Equation (11) is applicable to slag containing over 24%CaO while equation (12) is valid from zero %CaO
to saturation.
Unfortunately, in practice the phosphorus partition ratios are far from the values calculated for
equilibrium with carbon-free iron, because the oxygen potential of the slag-metal system is influenced by
decarburization. A limited correlation with the carbon content in the bath has been reported, although
other workers have suggested that extensive dephosphorization should be possible at high carbon levels,
provided that the slag is sufficiently basic.

On the other hand, the dependence of phosphorus distribution on the FeO content of slag in LD and QBOP is shown in Figure 2. A parameter kPS is defined as
kPS = (%P2O5)/[%P](1 + (%SiO2)) = ((%FeO),B) .....(13)
where B is basicity; for B>2.5, kPS is found to be independent of B.
The distribution of phosphorus is also found to be related to the content of carbon in steel at the time of
tapping; owing to lower carbon levels achieved in bottom-blown process, the phosphorus distribution is
expected to be better than in LD. In general, high basicity and the low temperature of slag (irrespective of
the FeO content) favor dephosphorization.

Figure 2: Effect of FeO content of slag on phosphorus distribution and log kPS value

Sulfur removal
Sulfur transfer takes place through the following reactions:
[S] + (O2)g = (SO2)g .....(14)
It is found that approximately 15-25% of dissolved sulfur is directly oxidized into the gaseous phase due
to the turbulent and oxidizing conditions existing in the jet impact zone.
In Basic Oxygen Furnace, the metal desulphurization proceeds slowly because it is a diffusion process. It
may be speeded up by improving the bath mixing and increasing the temperature, fluidity and basicity of
the slag, and the activity of sulfur. At the initial stage of the heat, when the metal is rich in carbon and
silicon, the activity of sulfur is high. Besides, part of sulfur is removed at the initial stages of the process
when the temperature of melt is still relatively low through its reaction with manganese:
[Mn] + [S] = (MnS) .....(15)

A rise in the concentration of iron oxides in the slag promotes dissolution of lime, and therefore favors
desulphurization. But the secondary and most intensive desulphurization occurs at the end and of the heat
when the lime dissolves in the slag with a maximum rate and the slag basicity reaches B=2.8 and more.
Thus the total desulphurization of the metal is mainly decided by the basicity of the homogeneous final
slag which is formed in the oxygen converter process during the last minutes of metal blowing.
With an increase of slag basicity, the residual concentration of sulfur in metal bath becomes lower, so that
the coefficient of sulfur distribution between slag and metal can be raised up to 10. The greater the bulk of
slag is the largest part of the sulfur will pass into slag at the same sulfur distribution coefficient. But it is
not beneficial to form a very large bulk of slag, since this increases the iron loss due to burning, causes
splashings and rapid wear of the lining.
In a steel plant, regression equations based on operational data are employed to predict the end point
sulfur within acceptable limits. One such equation, for example is
(%S)/[S] = 1.42B 0.13(%FeO) + 0.89 .....(16)
The equation 16 shows the beneficial influence of slag basicity and the retarding influence of FeO on
sulfur distribution. A large number of such correlations are reported in the literature, but they are suitable
and applicable to a local situation only.

Thermodynamics of TiN Formation in Melts:

Part One
Abstract: In steelmaking process, a strong nitride forming element such as titanium is often added to
stabilize nitrogen and improve mechanical properties of steel through the grain refinement during hot
rolling.
Recently, the formation of titanium nitride as a secondary inclusion precipitated during solidification
received great interest because it is known to help the formation of equi-axed cast structure. On the other
hand, titanium nitride formed in liquid steel can agglomerate and cause a nozzle clogging during
continuous casting and surface quality problems of final products. In order to control the formation
titanium nitride in various grades of steel, it is essential to have accurate thermodynamic data of titanium
and nitrogen in steel.

ntroduction
In steelmaking process, a strong nitride forming element such as titanium is often added to stabilize
nitrogen and improve mechanical properties of steel through the grain refinement during hot rolling.
Recently, the formation of titanium nitride as a secondary inclusion precipitated during solidification
received great interest because it is known to help the formation of equi-axed cast structure. On the other
hand, titanium nitride formed in liquid steel can agglomerate and cause a nozzle clogging during
continuous casting and surface quality problems of final products. In order to control the formation
titanium nitride in various grades of steel, it is essential to have accurate thermodynamic data of titanium
and nitrogen in steels containing other alloying elements.
The reaction equilibrium for the formation of TiN in liquid iron can be written as:
TiN(S) = [Ti] + [N] .......... (1)
G = 379000 - 149 T J .......... (2)
K = hTi hN / TiN= fTi fN[%Ti] [%N] .......... (3)
Where:

K is the equilibrium constant for reaction 1

hTi hN activity of titanium and nitrogen relative to 1 mass% standard state in liquid iron
respectively
fTi and fN interaction coefficient titanium and nitrogen, respectively.

During deoxidation process, the interaction parameter between titanium and silicon in liquid steels is
important, because recently complex deoxidation by silicon and titanium is carried out in many grades of
steels including stainless steels. The results from many investigations using similar technique show a
large disagreement on the effect of silicon on the activity coefficient of titanium.
In the other hand, it is well known that the thermodynamic data of titanium in Fe-Cr melts are not
consistent in the literature, and little information is available at temperatures other than 1600C.
Because of the all mentioned above, the purpose of the investigations by J.J.Pak et. al., where to obtain
reliable thermodynamic data of titanium and nitrogen/silicon in both Fe-Cr and Fe-Si melts as a function
of temperature, in order to predict under what condition titanium nitride will form during steel processing.
The metal-nitride-gas equilibration experiments were carried out to determine soluble titanium and
nitrogen in Fe-Cr and Fe-Si melts respectively in the presence of pure solid TiN under various nitrogen
pressures. The experiment was carried out in a graphite resistance furnace in the temperature range of
1570-1650C.

Activity Coefficient of Titanium

Table 1 and 2 summarizes the experimental results of metal-nitride-gas equilibrium for Fe-Cr and Fe-Si
melts at 1843-1923 K (1570-1650C).
During the equilibration experiments, the following equilibrium can be established:
TiN(S) = [Ti] + N2(g) .......... (4)
G = 375 402 - 172.89 T J .......... (5)
K= hTi PN2 / TiN = fTi[%Ti] PN2 .......... (6)
Where K is the equilibrium constant for reaction (1), and hTi is the activity of titanium relative to 1 mass%
standard state in liquid iron, fTi is the activity coefficient of titanium and PN2 is the nitrogen partial
pressure in the gas phase. Under the experimental condition, the activity of titanium nitride is unity.

Table 1: Experimental results of metal-nitride gas equilibrium in Fe-Si melts

Table 2: Experimental results of metal-nitride gas equilibrium in Fe-Cr melts

The equilibrium constant K can be rewritten as the following relation using the appropriate interaction
parameters:
log KFe-Cr = log fTi + log[%Ti] + log PN2 =
= eCrTi[%Cr] + rCrTi[%Cr]2 + eTiTi[%Ti] + eNTi[%N] + eOTi[%O] + log[%Ti] + log PN2 .......... (7)
Then
log fCrTi = eCrTi[%Cr] + rCrTi[%Cr]2 =
= log K11 - eTiTi[%Ti] - eNTi[%N] - eOTi[%O] - log[%Ti] - log PN2 .......... (8)
Where fCrTi is the interaction coefficient of Cr on Ti in liquid iron, and eCrTi and rCrTi are the first and second
order interaction parameters of Cr on Ti, respectively.
In the same way, for Fe-Si melts, the equilibrium constant K can be rewritten as the following relation
using the appropriate interaction parameters:
log KFe-Si = log fTi + log[%Ti] + log PN2 =
= eSiTi[%Si] + rSiTi[%Si]2 + eTiTi[%Ti] + eNTi[%N] + log[%Ti] + log PN2 .......... (9)
Then

log fSiTi = eSiTi[%Si] + rSiTi[%Si]2 =

= log K12 - eTiTi[%Ti] - eNTi[%N] - log[%Ti] - log PN2 .......... (10)
Where fSiTi is the interaction coefficient of Si on Ti and is a measure of the effect of specific concentration
of Si on the behavior of Ti in dilute solution in liquid iron, and eSiTi and rSiTi are the first and second order
interaction parameters of Si on Ti, respectively.
The Tables 3 and 4 show the values of eCrTi; rCrTi, eSiTi; rSiTi in Eq.9 and Eq.10 given from many
experimental results of equilibrium titanium and nitrogen contents as a function of both chromium
content in Fe-Cr-Ti-N melts and silicon content in Fe-Si-Ti-N melts.
Table 3: Interaction parameters of Si on Ti and N
Temperature
1873 K
Dependency
-0.0256
eSiTi

177.5/T-0.120

2.1
1.431
0.064

rSiTi

0
-0.00065
0.0491

eSiN

-286.2/T + 0.202

0.047
0.048
-0.038

Si
N

r
0
Table 4: Interaction parameters of Cr on Ti and N
Temperature
1873 K
Dependency
0.028

1196/T-0.61

0.055
Cr
Ti

0.022
0.016
0.024
0

rCrTi

-0.0001
0.0005
-0.045

- 850/T + 0.409

-0.047
eCrN

-0.046

- 164/T - 0.0415

-0.045
0
Cr
N

-0.0004
0.00032

1.67/T - 0.0006

Thermodynamics of TiN Formation in Melts:

Part Two

Abstract: In steelmaking process, a strong nitride forming element such as titanium is often added to
stabilize nitrogen and improve mechanical properties of steel through the grain refinement during hot
rolling.
The validity of TiN thermodynamic parameters can be examined by constructing the stability diagram of
TiN for both Fe-Cr and Fe-Si melts and by observing the formation of primary and secondary TiN
inclusions at controlled titanium and nitrogen contents in melt.

TiN Stability Diagram

The stability diagrams for TiN indicate the conditions under which TiN inclusions will form in melts.
Using the thermodynamic parameters obtained in the many studies and the data available in literature, it is
possible to construct the TiN stability diagram for both a Fe-1%Si-Ti-N melt and Fe-11%Cr-0.4%Si-Ti-N
as shown in Figures 1 and 3.
In order to check the validity of the TiN stability diagram, the soluble titanium and nitrogen contents
analyzed in metal samples for Fe-11%Cr-Ti-N alloy at 1873 K and 1800 K are shown as points D, E and
F in Figure 1.

Figure 1: Stability diagram of TiN for Fe-11%Cr-Ti-N melt.

According to the stability diagram, all samples Fe-11%Cr-Ti-N melts would not form TiN inclusions at
1873 K. However, as the metal temperature decreases to 1800 K, it can be expected that TiN precipitate
as secondary inclusions for samples D and E. Inclusion analysis by EPMA /Electron-ProbeMicroanalysis/ for the samples could not identify any primary TiN inclusions. However, as shown in
Figure 2, TEM-EDS /Transmission Electron Microscopy and Energy-Dispersive-Spectroskopy/ analysis
on sample D and E identified fine secondary TiN inclusons of 0.3-0.5 m precipitated from the melts on
cooling. TiN inclusions were not observed in sample F.
The above results verify that thermodynamics parameters of chromium on titanium and nitrogen
determined in the present study are valid for the thermodynamic calculation of TiN formation in Fe-Cr-TiN system as a function of temperature.

Figure 2: TEM image and EDS data of inclusions in Fe-11%Cr-Ti-N melt.

The Figure 3 shows the stability diagram for a Fe-1%Si-Ti-N melt at 1873 K.

Figure 3: Stability diagram of TiN for Fe-1%Si-Ti-N melt at 1873 K.

It is apparent that there is a large discrepancy in predicting nitrogen and titanium contents for the
formation of TiN in iron melt containing 1 mass% Si.
In order to resolve this discrepancy, a critical experiment was carried out to see under what conditions
TiN forms in Fe-1%Si-Ti-N melt. Four Fe-1%Si-Ti samples containing different titanium contents were
equilibrated with an Ar-10%N2 atmosphere at 1873 K for 12 h. Titanium nitride pellet was not added in
this experiment. After the equilibration, the samples were water quenched, and analyzed for soluble
titanium and nitrogen contents (points A, B, C and D in Figure 3).
According to the line 4 in Figure 2 calculated using the eSiTi value determined in many investigations, the
melts with titanium and nitrogen contents of points A, B and C would not form TiN, whereas the lines 1
and 2 predict that TiN would form readily under all conditions. Inclusion analysis on metal samples by
EPMA identified all inclusions in samples D as TiN precipitates as shown in Figure 4. However,
inclusions in order samples (A, B and C) were identified as SiO2-TiO2 type inclusions. Figure 5 shows the
SEM /Scanning Electron Microscope/ image of TiN precipitates in sample D.

Figure 4: SEM image and EPMA analysis of inclusions in Fe-1%Si-Ti-N melt.

Figure 5: SEM image of TiN precipitate in sample D.

Conclusion
The validity of TiN thermodynamic parameters can be examined by constructing the stability diagram of
TiN for both Fe-Cr and Fe-Si melts and by observing the formation of primary and secondary TiN
inclusions at controlled titanium and nitrogen contents in melt.

Control of Sulfur in Melts: Part One

Abstract: Sulfur has a strong surface activity both in binary (Fe-S) and ternary (Fe-C-S, Fe-Si-S) alloys.
It has been concluded from the results of numerous studies that sulfur can exist in two forms in molten
iron: in one case it forms an interstitial solutions, and in other partially substitutional solutions. It has been
found that the activity of sulfur increase substantially when carbon and silicon are present in the melt.
This explains why pig iron can be desulfurized more readily than steel.
Sulfur (S) is a typical metalloid. The radius of sulfur atom is 1.05 . It easily acquires two electrons to
form an ion S2-. The coefficient of diffusion of sulfur in liquid iron is 0.74x10-4, 13x10-4, 1.9x10-5 cm/s,
according to various experimental data. Sulfur has a strong surface activity both in binary (Fe-S) and
ternary (Fe-C-S, Fe-Si-S) alloys. It has been concluded from the results of numerous studies that sulfur
can exist in two forms in molten iron: in one case it forms an interstitial solution, and in other partially
substitutional solutions. It has been found that the activity of sulfur increase substantially when carbon
and silicon are present in the melt. This explains why pig iron can be desulfurized more readily than steel.
A good understanding of the desulphurization of hot metal and liquid steel has been developed in terms of
slag-metal reactions, based on a number of studies of the partition of sulfur between liquid slag and liquid
iron. These results show that a highly basic slag, high temperature and reducing conditions enhance
desulphurization via slag-metal reactions.

Sulfur Equilibrium between Liquid Iron and Slag

The desulphurization of liquid iron with slag may be examined on the basis of the following reaction (1),
in which the equilibrium constant can be expressed by equation (2).
[S] + (O2-) = (S2-) + [O] .......... (1)
log K1 = as2-. ao / as. ao2- .......... (2)
where,

ao, as: the activities of oxygen and sulfur in liquid iron, respectively
ao2-, as2-: the activities of oxygen and sulfur ions in slag, respectively.

The sulfur partition ratio between metal and slag is given by equation (3) according to reaction (1).
LS = (wt%S) / [wt%S] = K1 ao2- fs / ao fs2- .......... (3)
where,

fs, fs2- : the activity coefficients of sulfur in liquid iron and slag, respectively.

Since the values of K1, ao2- and fs2- cannot be determined experimentally, the sulfide capacity is defined as
equation (5) on the basis of reaction (4) and is utilized for the examination of desulphurization in iron and
steel making processes.
S2 + (O2-) = (S2-) + O2 .......... (4)
CS = (wt%S) (PO2 / Ps) = K4 ao2- / fs2- .......... (5)
where,

PO2 and Ps are the oxygen and sulfur partial pressure in atm;
K4 the equilibrium constant of reaction (4).

In order to calculate the value of CS, the equilibrium constants of reactions (6) and (7) are substituted into
equation (5), and equation (8) is obtained.

 O2 = [O] .......... (6)

S2 = [S] .......... (7)
log Cs = log (wt % S) ao / as + 936 / T-1.375 .......... (8)
By the use of the interaction coefficients of sulfur and oxygen in liquid iron, the values of CS can be
calculated from equation (8).
As an illustration, the calculation of sulfide capacity (CS) has been given for CaO-MgO-Al2O3-SiO2 ladle
slags.
In order to examine the relationship between CS and composition of slag, the following relationship is
assumed to hold at certain temperatures.
log CS = (NCaO + KMgO NMgO + KAl2O3 NAl2O3 + KSiO2 NSiO2)+ .......... (9)
where:

, : the constants
Ni, Ki: the mole fraction and the lime equivalent coefficient of i-component in the slag phase,
respectively.

At 1600C, the values of KMgO, KAl2O3 and KSiO2 determined by trial and error are 0.1, -0.8 and -1.0,
respectively. As shown in Figure 1, there are linear relations between log Cs and (NCaO + 0.1 NMgO 0.8
NAl2O3 NSiO2) at 1575, 1600 and 1650C.

Figure 1: Plot of the log Cs against NCaO + 0.1NMgO 0.8NAl2O3 NSiO2 at 1575, 1600 and 1650C
The three lines obtained by the method of least squares are shown in the figure. The intercepts of the lines
were determined by the use of the slope at 1600C because the most runs were done at this temperature.
The following equation was obtained as a function of temperature.
log CS = 3.44 (NCaO +0.1NMgO 0.8NAl2O3 NSiO2) - 9894 / T+2.05 .......... (10)
The observed values of log CS with the correlation coefficient (R) of 0.99 and the standard deviation ()
of 0.044 can well be expressed by the above equation.
On the other hand, log LS may be expressed by the following general equation derived from equations.
(3), (8) and (10).

log LS = KiNi - log [wt%O] - .......... (11)

where,

KiNi = NCaO +0.1NMgO 0.8NAl2O3 NSiO2.

The experimental data were arranged by the method of least squares according to equation (11) and the
following relationship was obtained.
log LS = 3.44 KiNi - log [wt% O] - 10 980 / T+3.50 .......... (12)

Relationship Between Sulfide Capacity and Theoretical Optical Basicity

Duffy and Ingram defined the theoretical optical basicity () as follows:
= (xi / fi) .......... (13)
where, xi, fi : the equivalent cationic fraction and the basicity moderating parameter for the constituent
cation i, respectively.
It was verified by them that fi can be expressed by the Pauling's electronegativity xi as follows:
fi =1.36 (xi -0.26) .......... (14)
It was also found by Duffy and Ingram that log CS are linearly correlated to the theoretical optical
basicity.
As an illustration of the above mentioned the experimental results performed on ladle CaO-MgO-Al2O3SiO2 slags has been given. The values of log CS are plotted against the optical basicities at 1575, 1600 and
1650C, as shown in Figure 2.

Figure 2: Plot of log CS against theoretical optical basicity

The slopes and intercepts of the lines were determined by the method of least squares, and the following
linear relationship was obtained as a function of temperature.
log CS = 14.20 - 9 894 / T -7.55 .......... (15)
As described above, it can be seen that both the sum of lime equivalent and the optical basicity are able to
be used as parameters for the representation of sulfide capacity. From the relationship between these two
parameters, the linear equation (16) from regression was obtained.

 = 0.24(NCaO + 0.1NMgO 0.8NAl2O3 NSiO2) + 0.67 .......... (16)

The correlation coefficient (R) is larger than 0.99, and the standard deviation () is smaller than 0.01. This
shows that the two parameters have almost the same character for the representation of sulfide capacity of
slag.

Equilibrium of Oxygen Partition between Metal and Slag

It is well known that the oxygen potential exerts a large influence on the sulfur partition between metal
and slag. The equilibrium of reaction (17) was determined by the use of the value of the equilibrium
constant (18) reported in literature.
(FeO) = [Fe] + [O] .......... (17)
log K17 = log ao / aFeO = -6 150 / T + 2.604 .......... (18)
Equation (18) may be modified to the following equation.
log [wt%O] = log NFeO + log FeO - log fo - 6 150 / T + 2.604 .......... (19)
where FeO is the activity coefficient of FeO on the basis of mole fraction.
Since log FeO is a function of temperature and slag composition, log [wt%O] can be expressed by an
equation including the term of log NFeO, then the following relationship was obtained.
log [wt%O] = 0.905 log NFeO -0.15 KiNi - 6 340 / T + 3.115 .......... (20)
where, KiNi = NCaO + 0.1NMgO 0.8NAl2O3 NSiO2.
As shown in Figure 3, the observed values of log [wt% O] agree well with the values calculated from the
equation (20). By substituting equation (20) into equation (12), equation (21) is derived:
log LS = 3.59 KiNi -0.905 log NFeO 4 640 / T + 0.385 .......... (21)
The above equation can conveniently be used for the estimation of the sulfur partition between liquid iron
and slag in which the oxygen content in liquid iron is not analyzed. Next, the values of FeO calculated
from the equation (19) were arranged by the way similar to that described previously, and the following
relationship was obtained.

Figure 3: Comparison of the observed log [wt%O] with calculated log [wt%O] from the equation (20)

Reoxidation of Steels: Part One

Abstract: The internal cleanliness of steel is determined by the composition, size, number and
distribution of its inclusions. It should be strictly controlled to ensure the castability of the liquid steel as
well as the functional properties of the final product. The inclusions are formed during converter tap,
ladle treatment and continuous casting of the steel and they can be oxides, sulfides and nitrides.
The oxides are formed by the reaction of dissolved reactive metals and oxygen, either dissolved in the
steel or originating from the atmosphere, refractories or slags. Erosion of the refractories and slag
dispersion can also be sources of new inclusions.

Introduction
The internal cleanliness of steel is determined by the composition, size, number and distribution of its
inclusions. It should be strictly controlled to ensure the castability of the liquid steel as well as the
functional properties of the final product. The inclusions are formed during converter tap, ladle treatment
and continuous casting of the steel and they can be oxides, sulfides and nitrides. The oxides are formed by
the reaction of dissolved reactive metals and oxygen, either dissolved in the steel or originating from the
atmosphere, refractories or slags. Erosion of the refractories and slag dispersion can also be sources of
new inclusions.
Most of the oxide inclusions are formed during deoxidation and subsequent reoxidation processes. Liquid
steel processing includes measures that remove the inclusions to the slag, such as argon stirring of the
ladle and flow pattern control in tundish. Therefore, the composition of the ladle, the tundish and the
mould slags should be optimized to pick up and dissolve inclusions, although a compromise with the
other functions of the slag is necessary. The formation of new oxides is to be avoided because entrainment
of these particles by the steel deteriorates internal cleanliness. The steel is therefore protected from
reoxidation as adequately as possible, e.g. by shrouding the steel stream from ladle to tundish and tundish
to mould using nozzles, by using stable refractory materials and by utilizing slags low in FeO+MnO
content.
In ladle refining processes, (FetO + MnO) content in slag should be lowered less than 1 wt% for the
effective desulphurization and the suppression of the steel reoxidation. This brings about an increase in
production cost and processing time because of the excessive injection of raw materials. Decreasing the
activity coefficients of FetO and MnO is an alternative solution for controlling the activities of the
reducible oxides while maintaining high (FetO + MnO) content.
As an illustration of the reoxidation of steel by adding the usual deoxidizers (Si and Al) are showed in this
article.

Reoxidation of Steel By Adding Silicon

Silicon is a strong deoxidizer. If [%Si] 0.2, [%C] 0.15, and the temperature of the melt is 1873 K, then
the following reaction is possible:
.......... (1)
The equilibrium constant of the reaction (1) is

.......... (2)
If the standard state is solid silica, then in the thermodynamic calculation of deoxidation of steel by
silicon aSiO2 is taken as being equal to one. According to Kramarov if the slag is saturated with silica then:

.......... (3)
So the deoxidation ability of silicon depends on its concentration and the temperature of the metal, but
also on the activity aSiO2. At high temperature and the some value of [%Si], [%Mn] and [%C], its
deoxidation ability is something smaller than that of carbon, but considerably higher than manganese.
At some point during the increase in the concentration of silicon in the Fe-Si melt the minimum
concentration of oxygen [%O]min is obtained; any further increase in [%Si] results in an increase of
[%O]. At first sight this suggests that the product of the activity coefficients (foSi)2 fSiSi decrease faster than
the increase of [%Si]. In agreement with the expression for the equilibrium constant (2), the extreme
value for the concentration of silicon [%Si]extr. corresponds to the minimum concentration of [%O]min.
When calculating the critical value of [%O]min. and [%Si]extr., it is necessary to express equation (2) in the
following way
ln[%O] = ln aSiO2 - ln KSi-O - ln [%Si] - ln fSiSi - ln fOSi .......... (4)
The logarithms of the coefficients of activity are:
.......... (5)
.......... (6)
and the interaction parameters are eOSi = -0.133 and eSiSi = 0.098. The interaction parameters eO0 and eSi0
are neglected because the concentration of oxygen is relatively small (log fOO 0, log fSiO = eSiO [%O] 0,
and follows fOO 1 and fSiO 1), and the activity aSiO2 = 1.
To obtain [%Si]extr, it is necessary to take the first derivative of the concentration of oxygen divided by the
concentration of silicon and set the equation equal to zero under specific conditions:

.......... (7)
The second derivative is greater than zero:

.......... (8)
Consequently, the function has a minimum. The concentration of silicon at which [%O] is a minimum:

.......... (9)
On the basis of the quote d value of the interaction parameters for T=1873 K and aSiO2=1 [%Si]extr. a value
of 2.59% is obtained. In that case fSiSi = 1.794 and fOSi = 0.452. For steel melts there is also the influence of
the other elements on fSi and fO. At 1873 K the equilibrium constant KSi-O = 25099. The minimum
concentration of oxygen in the melt is:

.......... (10)
By inserting reasonable values into equation (10) a minimum concentration of oxygen [%O]min = 6.5 x 103 % is obtained.

Reoxidation of Steel By Adding Aluminum

The deoxidation of steel by aluminum proceeds according to there action:
.......... (11)
The equilibrium constant may be determined from:

.......... (12)
At 1873 K, the equilibrium constant is KAl-O = 4.9 x 1013. In the calculation it is assumed that aAl2O3 = 1,
because at small values of [%Al] (0.001-0.01) the equilibrium concentration (%FeO) in the slag is
neglected, so the products of deoxidation are solid Al2O3 or an oxide phase saturated with alumina.
The coefficient of activity of aluminum fAl = fAlAl fAlO = O 1, and the coefficient of oxygen fO = fOO fOAl =
fOAl, which is an approximation, because the influence of the other elements present on fO is very strong,
and fO is <1. The equilibrium concentration of oxygen in the melt may be expressed with:

.......... (13)
An analysis of the equation (13) shows that at some increment of the concentration of aluminum the
activity factor fOAl decreases faster than [%Al]2/3 increases. The result is that at some value of [%Al] the
[%O]min. is obtained. A further increase in [%Al] results in an increase of [%O]. To obtain [%Al]extr., the
first derivative of the logarithm of the concentration of oxygen divided by the concentration of aluminum
must be set equal to zero:

.......... (14)
.......... (15)
According to Kulikov, interaction parameter e0Al = -1.17, which corresponds to [%Al]extr. = 0.248.
According to formula (13) the minimum concentration of oxygen [%O]min = 1.35 x 10-4 % is obtained.