2.

Physico-Chemical Principles of Steelmaking Processes

2.4 SLAGS IN STEELMAKING PROCESSES

2.4.1 INTRODUCTION
In steelmaking, slag is mostly a solution of oxides and sulphides in the molten state, and the multi-
crystalline phase in the solid state.
Rate of reaction and quality of product is determined largely by controlled additions to the slag.
• These additions consist of oxygen in the form of ore or gaseous oxygen
• Together with more stable ‘slag-forming’ oxides such as SiO2, CaO and MgO, they oxidise
impurities from the melt
The slag produces a correct environment to absorb product of oxidation at a suitably low level of
activity and, thus, form a suitable carrier for the reactive FeO and a sink for the P and S removed from
the metal.
Although the slag has very different purposes in ironmaking and steelmaking processes, it plays a
dominant rule in both types of processes.
• The importance of slag has long been appreciated and this is succinctly summarised by the
steelmaking proverb: “look after your slag and the metal will look after itself.”

2.4.1.1 Source of slag

The main sources of slag in the steelmaking furnace are as follows:
1. The products of oxidation of impurities (Si, Mn, P, Cr, etc.) introduced into the furnace together
with pig iron and scrap: SiO2, MnO, P2O5, Cr2O3, etc.
2. The products of erosion of the furnace lining: SiO2 (from silica lining), MgO (from magnesite
lining), MgO and Cr2O3 (from chrome-magnesite lining), etc.
3. Impurities (sand, dirt, mixer slag, etc.) brought in with the charge: SiO2 and Al2O3 (from sand
and clay), MnS (from mixer slag), etc.
4. Rust of scrap, especially when light-weight scrap (bundle-scrap, trimmings, roof iron, etc.) is
used: FeO, Fe2O3, Fe(OH)2, etc.
5. Additional materials and oxidisers (limestone, lime, bauxite, fluorspar, iron and manganese ores,
etc.): CaCO3, CaO, Al2O3, CaF2, Fe2O3, Fe3O4, MnO2, etc.

2.4.1.2 Role of slag

During melting and tapping, the molten metal is in continuous contact and interaction with the slag.
• The composition, temperature, fluidity and other parameters of slag have a decisive effect on
the course of the heat and the quality of the final metal.
The prime objective of a steelmaker is to remove harmful impurities (usually S and P) from the metal.
• The problem is solved by removing these impurities to the slag and by forming conditions
which prevent their passage back to metal.
By varying the composition, temperature and certain properties of the slag, it is possible to control the
concentrations of Mn, C and Si and other desirable elements in the metal.
For that reason, the steel maker must form slag of the desired composition and proper thickness if he is
aimed at producing high-quality steel.

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 Rashid . Ferrous Production Metallurgy

The slag should meet the following requirements:

1. it should ensure the desired degree of refinement of the metal from harmful impurities and act as a
sink for impurities;
2. during the oxidation periods of a heat, slag must ensure intensive passage of oxygen from furnace
atmosphere to metal;
3. during other periods of a heat and in the ladle upon tapping, slag should prevent passage of oxygen
from atmosphere to metal;
4. the slag must prevent the passage of gases (nitrogen and hydrogen) from atmosphere to metal;
5. the slag being skimmed off from the furnace should not contain much of iron so as not lower the
degree of utilisation of iron in the charge;
6. during melting, slag must act as a thermal barrier to prevent heat transfer from molten steel to the
surroundings;
7. during teeming, slag must prevent the cooling of the metal in the ladle;
8. in many cases, the composition of slag should meet certain special requirements, for instance,
when the slag will be used as a building or road construction material, as a fertilizer, or as a
material for extraction of valuable impurities, such as V, Ti, Cr, etc.
Slag of the desired composition is formed by introducing a calculated quantity of additions (slag
formers).
When needed, a slagging-off procedure is carried out, i.e. a definite amount of slag (sometimes almost
100%) is removed from the furnace by skimming-off and new slag of the desired composition and
properties is formed by giving measured quantities of particular additions.
• In some cases, skimming-off and slag removal may be carried out twice or even three times.

2.4.1.3 Slag composition and properties control

The diverse functions of slag mention above require that slag should possess certain physical (density,
melting point, viscosity) and chemical properties (basicity, oxidation potential).
• Both physical and chemical properties are controlled by composition and structure of slag.
• In steelmaking slag is predominantly a mixture of oxides with small amount of sulphides and
phosphides. The oxides are either acidic or basic in nature.
The most popular method of slag control is to take a sample of slag by a spoon and perform the
chemical analysis.
• Slag is usually analysed for the concentration of FeO and MnO. Besides, it may be analysed
for SiO2, CaO, Mg, etc. when needed.
In another method, slag is controlled by the appearance and fracture of solidified slag cakes.
• If particular grades of steel are being made in a furnace by an established technology, visual
control makes it possible to detect rather easily any departures from the correct technology.
The slag thickness or viscosity plays an essential part in the processes of interaction between metal
and slag, especially in cases when the rate of the process is limited by the rate of diffusion.
• Diffusion is more intensive when the slag has a lower viscosity.
Besides composition and temperature of slag, viscosity also depends appreciably on the homogeneity
of slag.
• In many cases, a heat may be far from being homogeneous, since it may contain an
appreciable quantity of undissolved solid particles of high melting oxides.
• For that reason, it is essential to measure the fluidity of slag

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 2. Physico-Chemical Principles of Steelmaking Processes

It should be noted that the viscosity of slag is usually several times that of molten steel.
• For instance, at a temperature of 1600 °C the viscosity of steel may be within 0.002-0.006 P
depending on composition, whereas the viscosity of rather free-flowing slags is not less than
0.02 P.

2.4.2 THE STRUCTURE AND COMPOSITION OF SLAG

Laboratory analyses of slag samples give information on the concentrations of CaO, SiO2, FeO, etc. in
it in the solid state.
Molten slags are ionic in nature consisting of positively charged cations, and negatively charged
complex silicate, aluminate and phosphate anions.
• Cations present in slag include: Fe2+, Mn2+, Ca2+, Mg2+,
• Anions are: O2–, S2–, SiO44–, PO43–, FeO2–, Si2O76–.
The set of ions may be different depending on slag composition.
• For instance, acid slags may be supposed to contain the following complex ions which include
Si44– and O2–: SiO44–, Si2O76–, Si3O96–, Si4O128–, and Si6O1812–.
• More complex ions have larger dimensions (radii), which results in a higher viscosity of slag.
Slag analysis being given in terms of mass composition of either
• common oxides (FeO, CaO, MnO, SiO2, etc.) or
• pure elements [(Fe), (S), (P), etc.].
For instance, the steelmaker may be informed from the laboratory that the slag contains 15% FeO, 3%
Fe2O3, 9% MnO, 14% Fe and has a basicity of 2.7, etc.
Typical composition of slags in primary steelmaking processes for producing carbon and low alloy
steels varies within the following range, depending on the final carbon content of steel tapped, as:
40-60% CaO 1-2% Al2O3
10-28% SiO2 0-2% CaF2
5-35% FeO (total) 1-3% P2O5
2-8% MgO 0.1-2% S, and
1-8% MnO minor amounts of other impurities

All oxides found in the slag can be divided into three groups according to their chemical properties:
1. acid — SiO2, P2O5, TiO2, V2O5;
2. basic — CaO, MgO, FeO, MnO; and
3. amphoteric — Al2O3, Fe2O3, Cr2O3.

The mineral analysis of slags from various steelmaking processes has shown that the following
compounds are found most often in slag samples:
1. silicates: FeO.SiO2; (FeO)2.SiO2; MnO.SiO2; (MnO)2.SiO2; (CaO)2.SiO2; (CaO)3.SiO2;
MgO.SiO2; (MgO)2.SiO2; and Al2O3.SiO2
2. phosphates: (FeO)3.P2O5; (MnO)3.P2O5; (CaO)3.P2O5; (CaO)4.P2O5; (MgO)3.P2O5
3. aluminates: FeO.Al2O3; CaO.Al2O3; MgO.Al2O3
4. ferrites: FeO.Fe2O3; CaO.Fe2O3; (CaO)3.Fe2O3; (CaO)m.(Fe2O3)n

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 Rashid . Ferrous Production Metallurgy

Among more complex compounds which may be present in slags, the most common ones are
• monticellite CaO.RO.SiO2 (where R is Fe, Mn, Mg),
• merwinite 3CaO.RO.2SiO2,
• silicocarnotite 5CaO.P2O5.SiO2, and
• various spinels of mixed composition, of the type of calcium aluminoferrite
4CaO.A12O3.Fe2O3.
In high chromium slags, chrome spinel of varying composition, (FeO)n.(Cr2O3)m, may be present.
In high-magnesia slags, inclusions of hard periclase crystals, MgO, may be present in solid state.

2.4.3 PHYSICO-CHEMICAL ASPECTS OF STEELMAKING SLAG

2.4.3.1 Slag basicity

The steelmaker most often must deal with two groups of slags:
• acid (45-60% SiO2, 35-45% FeO + MnO), and
• basic (35-60% CaO + MgO, 10-25% FeO, 15-30% SiO2, and 5-20% MnO).
Basicity of slag is the ratio of mass concentrations (CaO)/(SiO2) or, in the case of high concentrations
of phosphorus, as the ratio (CaO)/[(SiO2)+(P2O5)].
• low-basic if (CaO)/(SiO2)  1.5;
• medium-basic if this ratio ranges from 1.6 to 2.5, and
• high-basic if the ratio is greater than 2.5.
It is extremely important to know the slag basicity and continuously control this parameter, since it
usually determines the most essential property of slag: its ability to extract from the metal and retain
such harmful impurities as sulphur or phosphorus.
Acid slags can be characterized by the ratio (SiO2)/[(FeO)+(MnO)] or (SiO2)/[(FeO)+(MnO)+(CaO)]
which is called the slag acidity.
In slag-metal reactions which involve desulphurization and dephosphorization, the concept of free
lime in slag is useful.
• Free lime in slag is that amount which is available after the formation of neutral compound
like 2CaO. SiO2, 3CaO. P2O5
Free lime (kg) = kg CaO – (112/60) kg SiO2 – (168/142) kg P2O5
For 100 ton hot metal with 1% silicon and 0.2% P the calculation shows that free CaO in slag would
be available when CaO content exceeds 4540 kg.

2.4.3.2 Oxidation and reduction potential of slag

Another important characteristic of slags is the degree of oxidation (i.e. ability to give up oxygen to
metal).
In many cases, the oxygen present in slag is needed for the oxidation of impurities (say, carbon) in the
metallic bath and in others, on the contrary, the passage of oxygen from slag to metal is undesirable.
• For these reasons, the degree of oxidation of slag should be controlled very carefully.
In the interaction between metal and slag
• Ferrous oxide (FeO) is the main oxidant, with trivalent iron (as Fe2O3) playing a part
• The ratio Fe3+/ Fe2+ depends on temperature, oxygen potential and slag composition.

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 2. Physico-Chemical Principles of Steelmaking Processes

In the formulation of the equilibrium constants of slag-metal reactions and the thermodynamic
activities of oxides in slags, the total iron dissolved in the slag as oxides is usually converted to the
stoichiometric formula FeO and denoted by FetO, thus
%FetO = %FeO (analyzed) + 0.9 x %Fe2O3 (analyzed)
or
%FetO = 1.286 x %Fe (total as oxides)
The equilibrium between FeO of slag and oxygen of steel
𝑎𝐹𝑒𝑂
(𝐹𝑒𝑂) = [𝐹𝑒] + [𝑂] ; 𝐾=
𝑎𝑂
indicates that the activity of oxygen in metal is proportional to the activity of FeO in slag.
In steelmaking plants, such as a converter or open-hearth furnace,
• an enormous quantity of gaseous oxidants is supplied to the bath surface, often in the form of
pure oxygen jets.
• solid oxidizers (iron ore, sinter, scale, etc.) are also given to the bath to intensify oxidation.
• For these reasons, concentration of iron oxides in slag at certain moments of a heat may be
rather high (sometimes up to 50%).

To find the oxidizing ability of basic slags various methods are practiced.
• Some of these involve determination of the total concentration of ferrous oxide in slag,
calculated in terms of oxygen, % (by mass) or the total concentration of iron oxides in slag, %
(by mass).
• The most reliable results are obtained by determining the activity of ferrous oxide in slag,
a(FeO); it may be either calculated or measured experimentally.
The activity of ferrous oxide a(FeO), in the acid slag is proportional to the concentration of FeO.
For basic slags, calculations of the activity of FeO are more intricate, i.e. 𝑎(𝐹𝑒𝑂) = 𝛾𝐹𝑒𝑂 . (𝐹𝑒𝑂).
• The activity coefficient 𝛾𝐹𝑒𝑂 depends on many factors, but mainly on slag basicity, Fig. 2.10.

Figure 2.10: Effect of slag basicity B on the activity coefficient FeO of iron oxide
in simple and complex slags at 1600 °C.

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 Rashid . Ferrous Production Metallurgy

2.4.3.3 Slag viscosity

Viscosity controls the fluidity of slag.
• The slag should be fluid so that it can be removed easily during tapping of steel.
In general viscosity of a slag is a function of
• temperature,
• composition and
• percent solid present in slag.
Viscosity 𝜂 of any slag composition decreases with the increase in temperature:
𝐸
𝜂 = 𝐴 exp ( )
𝑅𝑇
where A is an empirical constant and E is activation energy.
Viscosity of acid slags varies smoothly with temperature (‘long’ slags)
Viscosity of basic slags have a short temperature interval in which they pass from the liquid to solid
state (‘short’ slags); their viscosity increases sharply when temperature drops below 1500 °C.
• viscosity of basic slags depends substantially on the content of high-melting components, such
as Cr2O3 or MgO.

Figure 2.11: Effect of temperature on slag viscosity.

1 – basic slag, 2 – acid slag.

For a given temperature, addition of basic oxides decreases rapidly the viscosity of a slag which
contains SiO2 and P2O5
• The decrease in viscosity is greater with alkaline oxides like Na2O and fluorides like CaF2 as
compared with CaO and MgO.

Presence of solid particles in slag increases the viscosity of slag as shown in the following expression:
𝜂 = 𝜂0 (1 − 𝜖)−2.5
where 𝜖 is volume fraction of solids in slag.
• If volume fraction of the solid is in between 5% to 10%, viscosity of slag increases by 114%
to 130%.

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 2. Physico-Chemical Principles of Steelmaking Processes

2.4.3.4 Slag foaming

Foam is a dispersion of gas bubbles in a liquid.
• A liquid is said to be foaming when gas bubbles could not escape through the liquid and as a
result height of the liquid increases.
In steelmaking, 2 slag foaming reactions occur:
(FeO) + C = {CO} + [Fe] (deep inside the molten liquid)
[C] + [O] = {CO} (at the gas/slag interface)
In both the cases when the CO gas bubbles are unable to escape through the slag, the slag is said to be
foaming
• When C-O reaction occurs deep into the bath (i.e. the first reaction) then gas bubbles have
enough time to grow and can easily escape through the slag layer
• But, when the gas bubbles are produced by the second reaction, which occurs within the slag,
the bubble cannot escape due to smaller size
Slag foaming enhances the reaction area, so it is desirable to the extent that slag should not flow out of
the reactor.
The principal operational advantages of a foaming slag are:
1. Shielding of molten steel against atmospheric oxidation
2. Acting as a thermal barrier to prevent heat losses
3. Shielding of the refractory lining particularly in electric arc furnace
4. Controlling heat transfer from the post combustion flame
Quantitative measure of foaming is determined by the foaming index ():
∆ℎ ∆ℎ
 = 𝑠 =
𝑉𝑔 𝑄/𝐴
∆ℎ = increase in the height of the slag due to foaming
𝑉𝑔𝑠 = superficial gas velocity,
Q = gas flow rate,
A = area of the vessel

Low foaming index means

• easy escape of gas bubbles
• caused either by smaller gas bubbles or higher gas velocities
Foam life is directly proportional to foaming index.
• Increase in slag viscosity increases foaming index.
• Presence of solid particles and surface-active agents increases the foaming index.
• Addition of calcium fluoride decreases the foaming index by decreasing the viscosity of slag.
• Addition of carbonaceous materials will cause the foam to collapse, while alumina particles or
iron oxide pellets do not due to the different wetting characteristics with the slag.
Foaming index can be also calculated from the physical properties of slag and size of the gas bubble:
𝜂1.2
 =
𝛾 0.2 𝜌 𝐷𝑏0.9
𝜌 = slag density in kg/m3,
𝛾 = surface tension of slag in N/m, and
Db = gas bubble diameter in m.

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 Rashid . Ferrous Production Metallurgy

2.4.3 FORMATION SLAG IN STEELMAKING PROCESSES

The process of slag formation takes up a certain length of time.
• The processes of oxidation of impurities (silica, manganese, phosphorus, etc.) in the charge
into corresponding oxides occur at a definite rate.
• A certain spell of time is required to heat up and melt the charge (scrap, iron ore, lime, etc.).
• The processes of melting should be preceded by processes of decomposition of carbonates and
hydrates which are the main constituents of slag-forming materials, etc.
The use of slag-forming materials is determined by calculation in view of
• the composition of the charge materials,
• slag formers proper, and
• the slag of a desired composition that must be formed.
For instance, the charge of an open-hearth heat is calculated by considering
• the quantity of silica that can form by oxidation of the silicon present in pig iron and scrap,
• the quantity of silica that enters the furnace with iron ore and with other additions.
For the desired basicity (CaO/SiO2) of slag at the end of the heat, it is then possible to calculate the
quantity of lime or limestone that must be introduced to obtain this ratio.
• It should, however, be considered that the process of decomposition of say, limestone: CaCO3
→ CaO + CO2 takes up a certain length of time and that certain time is needed for lime lumps
to be smelted and to pass to the solution.
• Thus, if a slag sample is taken during heat, its composition will differ from the specification
and the slag sample will contain particles of undissolved lime.
• In practice, the quantity of lime that must be charged in the converter is almost twice that
value, since lime cannot be dissolved completely during the short time of the converter heat.
The rate of slag formation, i.e. the rate of passage of all slag constituents into the homogeneous liquid
solution, depends on many factors:
• temperature of the bath,
• composition of the first slag (formed at the beginning of heat),
• intensity of bath stirring,
• size of lumps of slag-forming materials,
• sequence of their charging, etc.
The productivity of modem steelmaking plants is very high (500 t/h or even more), the time of
blowing of a modem converter is less than 20 minutes; around 0.15 t of slag forms per ton of steel.
• This means that a slag mass of a few tens of tons must be formed in a few minutes.
If proper measures are not taken, it may turn out that the slag of the specified composition might not
be formed by the end of the heat, that harmful impurities would remain partially in the metal, etc.
Slag formation can be accelerated by several techniques:
• preliminary mixing and grinding of slag formers,
• artificial stirring of the bath,
• use of fluxed sinter with a definite proportion between CaO and SiO2 (basicity) instead of raw
iron ore,
• blowing of powdered slag formers into the metal,
Slag formation can also be carried out more quickly by timely addition of certain materials which can
lower the melting point of slag formers.
• For instance, addition of fluorspar (CaF2) or alumina (Al2O3) to a basic slag can lower the
melting point of the slag and increase its fluidity.

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 2. Physico-Chemical Principles of Steelmaking Processes

2.4.4 PROPERTIES OF SLAGS

The physical properties of slags depend of their composition and temperature.

Density

• slag density depends largely on the concentration of ‘heavy’ oxides in slags (Fig. 2.12).
• densities of slags will decrease with an increasing silica content.

Table 2.5: Density of some common

slag forming components.

Slag Components Density, g/cm3

SiO2 (tridymite) 2.26

CaO 3.40
MgO 3.65
MnO 4.50
Fe2O3 5.24
Figure 2.12: Density of basic slags
FeO 5.70 depending on concentration of iron and
manganese oxides

The density data for binary silicates are given in Fig. 2.13, while the data in Fig. 2.14 are for CaO–
MgO–Al2O3–SiO2 melts, relevant to neutral slags for steel refining in the ladle.

Figure 2.13: Densities of binary silicate melts. Figure 2.14: Densities of CaO–MgO–Al2O3–
SiO2 melt at 1550 °C.
(a) 0% MgO, CaO/Al2O3 = 1;
(b) 0% MgO, 5% Al2O3; (c) 5% MgO, 5%Al2O3.

Specific heat
• varies only within a narrow range [0.8-1.2 kJ/(kg K)]
• depends on composition and temperature of slag.

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 Rashid . Ferrous Production Metallurgy

Electrically conductivity
• possess a mixed type of (ionic and electrical) conductivity.
• electrical conductivity increases with an increasing slag basicity and increasing temperature.

Melting temperature
• Real slags are multi-component systems, so that their melting temperature cannot be found
easily by the melting points of the constituents.
• constitutional diagrams of ternary slag systems are referred
Addition of Al2O3 to a basic slag
• the melting temperature of the slag decreases (or, for a given temperature, the degree of
superheating of the slag above the melting temperature increases);
• the slag will be less thick and more fluid.
Addition of silica
• Increases melting point of an acid slag
• Decreases melting point of a basic slag

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