Lecture 4: Slag in steelmaking

Contents:
Preamble
The role of slag in steelmaking
Structure of pure oxides
Structure of pure silica
Network former and breaker oxides
Structure of slag
Keywords: Steelmaking, synthetic slag, Electric steelmaking, BOF steelmaking

Preamble

Slag plays a very important role in steelmaking to the extent that it is said that “make a slag and slag
makes steel”. Slag is a generic name and in steelmaking it is mostly a solution of oxides and sulphides in
the molten state and the multi-crystalline phases in the solid state.

Slag is a separate phase because

• It is lighter than molten steel and

• It is immiscible in steel
Slag is formed during refining of hot metal in which Si oxidizes to SiO2 , Mn to MnO, Fe to FeO, and P
to P2 O5 , and addition of oxides such as CaO, MgO, iron oxide, and others. The addition of oxides is done
to obtain desired physico-chemical properties of slag like melting point, basicity, viscosity etc. All these
oxides float on the surface of the molten steel. Synthetic slag is also used to absorb inclusions to
produce clean steel for certain applications.

The role of slag in steelmaking:

• It acts as a sink for impurities during refining of steel

• It controls oxidizing and reducing potential during refining through FeO content. Higher FeO
makes the slag oxidizing and lower FeO reducing
• It prevents passage of nitrogen and hydrogen from atmosphere to the molten steel
• It absorbs oxide/sulphide inclusions
 • It acts as a thermal barrier to prevent heat transfer from molten steel to the surrounding.
• It protects steel against re-oxidation
• It emulsifies hot metal and promotes carbon oxidation.
• In electric steelmaking slag prevents the radiation of heat of arc to the wails of the furnace and
roof
The above functions 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 amounts of sulphides and phosphides. The oxides are either acidic or basic in nature.
We will first consider the structure of pure oxides and then we discuss what happens on addition of one
type of oxide to the other.

Structure of pure oxides

In pure oxides

• Metallic cations are surrounded by oxygen ions in a three dimensional crystalline network
• Each cation is surrounded by the maximum number of anions in a closed packed structure, and
this number is called coordination number
• Cations of basic oxides such as CaO, MgO, FeO (Ca2+ , Mg 2+, Fe2+ ) etc. have radii smaller than
that of cations of SiO2 , Al2 O3
• Structure of an oxide depends on the ratio of radii of cations/anions as shown in the following
table

Structure CN Cation/anion Examples

Cubic 8 1 – 0.732
Octahedral 6 0.732 – 0.414 CaO, MgO, MnO, FeO etc.
Tetrahedral 4 0.414 – 0.225 SiO2, P2O5
Triangular 3 0.225 – 0.133

CN= Coordination number

As can be seen in the table the basic oxides have octahedral and acidic oxides tetrahedral structure.

Structure of pure silica

In silica, each atom of silicon is bonded with four oxygen atoms and each atom of oxygen is bonded with
two silicon atoms. The elemental tetrahedral of silica are joined at the vertices to give the hexagonal
network in three dimensions. The structure of pure solid and molten silica is shown in the figure

Figure 3.1: Structure of silica (a) solid and (b) molten

As seen in the figure 3.1a, each tetrahedron is joined at the vertex so as to obtain the three dimensional
hexagonal network. During melting the crystalline network of silica is broken by thermal agitation as
shown on figure 3.1b. Only at very high temperatures, molten silica consists of equal number of SiO4−
4

and Si4+ ions.

Network former and breaker oxides

It must also be understood that the bonding between cations and anions in acidic oxides like SiO2 and
P2 O5 is strong, and these simple ions group to form complex ions as (SiO4 )4− and(PO4 )3−. In slags,
these tend to form hexagonal network. These oxides are, therefore, called network formers or acids.
These acidic oxides can accept one or several oxygen ions.

Basic oxides like CaO, MgO, Na2 O, FeO dissociate and form simple ions like Ca2+ andO2−. All basic
oxides are donors of oxygen ions. These oxides are called network breakers, since they destroy the
hexagonal network of silica by reacting with it.

Structure of slag

Most slags are silicates. Pure silica has very high viscosity at the melting point. Addition of basic oxides
decreases the viscosity by breaking the hexagonal network of silica. Consider the addition of CaO to
molten silica. Calcium oxide dissociates to

CaO = Ca2+ + O2−

Each mole of CaO introduces one mole of oxygen ions in the hexagonal network of silica and can break
two vertices of the hexagonal structure of silica. By adding 2 moles of O2− for every mole of silica all the
four vertices are broken and we simply have Ca2+ and SiO4− as shown below

Note that Ca2+ can combine with two tetrahedrons

The reaction between alkaline base oxides, e.g. Na2O and SiO2 is as follows:

Na2 O + 2Na+ + O2− and

Since Na has one charge, each tetrahedron of silica will have Na ion attached to oxygen ion. As a result
one should expect more decrease in viscosity of silica on addition of alkaline base oxides as compared
with basic oxides.

The number of vertices destroyed depends on the fraction of basic oxide, i.e. the ratio of O/Si as
shown in the table

O:Si Formula Structure Equivalent silicate ions

2:1 SiO2 All corners of tetrahedron are shared (Si6O15)6− or (Si8O20)8−
5:2 MO.2SiO2 One broken link per tetrahedron (Si3O9)6− or (Si4O12)8−
3:2 MO.SiO2 Two broken link per tetrahedron (Si3O9)6−
7:2 3MO.2SiO2 Three broken link per tetrahedron (Si2O7)6−
4:1 2MO.SiO2 All link are broken (SiO4)4−
All the four vertices will be broken when 2 moles of CaO are added for each mole of silica. The resulting
slag would consist of Ca2+ and SiO4−
4 ions

References

L.Coudurier,D.W.Hopkins and I.wilkomirsky: Fundamentals of metallurgical processes

 Lecture 5: Physico-chemical properties of slag

Contents
Introduction
Viscosity
Basicity
Oxidation and reduction potential of slag
Slag foaming
Operational advantages
Quantification of slag foaming
Keywords: Foaming, electric steelmaking, basicity of slag, steelmaking reactions

Introduction:

This lecture discusses the physico-chemical properties of slag which are relevant in steelmaking. Slag is a
multi-component system and in steelmaking it consists of acidic oxides such as SiO2 and P2 O5 , and basic
oxides such as FeO, CaO, MgO etc. In some slags Al2 O3 is also present. In the last lecture we noted that
acidic oxides are network formers, whereas basic oxides are network breakers.

Viscosity:

Viscosity controls the fluidity of slag. The slag should be fluid so that it can be removed easily during
tapping of steel. In fact fluidity is inversely proportional to viscosity of slag. In general viscosity of a slag
is a function of temperature, composition and percent solid present in slag.

Viscosity of any slag composition decreases with the increase in temperature as given by the following
expression:

E
ηO = A exp � � (1)
RT

ηO is viscosity, A is an empirical constant, E is activation energy, T is temperature and R is gas constant.

For a given temperature, addition of basic oxides decreases rapidly the viscosity of a slag which contains
SiO2 and P2 O5 . The decrease in viscosity is greater with alkaline oxides like Na2 O and fluorides like
CaF2 as compared with CaO and MgO for the reasons discussed in lecture 3.
Alumina acts as a network breaker in an acidic slag and network former in a basic slag.

Presence of solid particles in slag increases the viscosity of slag as shown in the following expression:

η = ηO (1 − ϵ)−2.5 (2)

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%.

Basicity:

Basicity can be understood either from ionic or from molecular nature of slag. The ionic nature of slag
assumes slag to consist of ions. In slags, acidic oxides can accept one or several O2− ions, whereas a
basic slag is a donor of O2− ions. For example, 1 mole of SiO2 can accept 2 moles of O2− ions so that
each tetrahedron in hexagonal structure becomes independent of each other. Similarly each mole of
P2 O5 can accept 3 moles of O2− ions. Thus

SiO2 + 2O2− = SiO4−

4
� (3)
P2 O5 + 3O2− = 2(PO4 )3−

Amphoteric oxides behave as bases in presence of acid or as acids in presence of a base:

Al2 O3 + O2− = Al2 O2−

4
� (4)
Al2 O3 = 2 Al3+ + 3O2−

Bases can supply O2− ions

CaO = Ca2+ + O2−

In a neutral slag enough oxygen ions will be present to ensure that each tetrahedron remains
independent of each other. In binary CaO − SiO2 , slag will become neutral when CaO is 66.7%, which
corresponds to the formation of 2CaO. SiO2 . Slag will be basic only when CaO content is more than
66.7%. Basicity can be expressed in terms O2− ions which are in excess than that required, thus
satisfying the requirements of acidic oxides. In 100 g of slag

nO 2− = �nCaO + nMgO + nMnO + nFeO � + ⋯ − �2nSi O 2 + 3nP 2 O 5 + nAl 2O 3 � (5)

In industrial practice ionic definition of basicity is not useful; the molecular approach is more useful. The
molecular approach assumes slag to consist of chemical compounds. The basicity of slag is

weight % CaO
B = (6)
weight % SiO 2

In presence of different basic oxides, the different strength of the basic oxides should be considered. In
a slag which contains CaO, MgO, SiO2 and P2 O5 , the basicity is

(weight % CaO + 0.66 weight %MgO )

B = (7)
(weight % SiO 2 + weight % P 2 O 5 )

In slag/metal reactions which involve desulphurization and dephosphorization, the concept of free lime
in slag is useful. Free lime in CaO, SiO2 and P2 O5 slag is that amount which is available after the
formation of neutral compound like 2CaO. SiO2 , 3CaO. P2 O5

Free lime (Kg) = Kg CaO + 112/60Kg(SiO2 ) + 168/142Kg (P2 O5 ) (8)

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 4540Kg.

Oxidation and reduction potential of slag

It refers to the capability of slag to transfer oxygen to and from the molten steel bath. FeO content of
slag determines the oxidation potential of slag. Thus activity of FeO in slag is an important parameter.
The equilibrium between FeO of slag and oxygen of steel is

(FeO) = [Fe] + [O]

a (FeO )
K = a [O ]
(9)

The activity of oxygen in metal is proportional to the activity of FeO in slag.

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, slag foaming can
occur due to the following reactions:

(FeO) + C = {CO} + [Fe]

This reaction occurs within the slag. The other reaction

[C] + [O] = {CO}

This reaction occurs at the gas/metal interface. In both the cases when the CO gas bubbles are unable to
escape through the slag, the slag is said to be foaming. If the reaction between carbon and oxygen
occurs deep into the bath i.e. reaction 2 then gas bubbles have enough time to grow in size and can
easily escape through the slag layer as compared to when the gas bubbles are produced by reaction 2.
The reaction 2 occurs within the slag

Is slag foaming desirable? Yes to the extent that slag should not flow out of the reactor. Slag foaming
enhances the reaction area. In electric steelmaking foamy slag practice prevents the transfer of heat of
the arch to the refractory lining.

Operational advantages: A foaming slag

• Shields molten steel against atmospheric oxidation

• Acts as a thermal barrier to prevent heat losses
• Shields the refractory lining particularly in electric arc furnace
• Control heat transfer from the post combustion flame
Quantification of slag foaming:

Foaming index = Foam layer thickness/ average gas velocity

Low foaming index means easy escape of gas bubbles which can be obtained 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. Foaming index (FI) can be calculated from the physical properties of slag and size of the
gas bubble:

115 η o (1−ϵ)−2.5
FI = (ργ )0.5 (d b )0.9
(10)

ϵ = Volume fraction of solids in slag

ρ = Slag density kg/m3

γ = Surface tension of slag N/m

db = Gas bubble diameter in m

Calculate the foaming index slag of composition 60% CaO, 35% Al2 O3 and 5% Si O2 at 1773 K slag from
the following data:

Kg Kg
ηo = 3.5 , ρ = 2500 γ = 1.1 N/m and db = 0.005 m and 0.01m.
ms m3,

Substituting the value of the variables in eq. 10 we get

FI = 904s for db = 0.005 m and 485 s for db = 0.01 m.

If the volume fraction of solid particles in slag is 0.1

FI = 1175 s for db = 0.005 m and 631 s for db = 0.01 m.

Note that foaming index increases to 1.3 times due to presence of solid particles in slag.

Consider a slag of composition 55% CaO, 35% Al2 O3 and 1% Ca F2 at 1873 K whose
ηo = 0.7 Kg/ms, ρ = 2700 Kg/m3 and γ = 1.4 N/m and db = 0.01m. This slag would have foaming
index 9s. Foaming tendency decreases drastically due to production of CaF2 in slag.

Reference to lectures 3 and 4

A.Ghosh and A.Chatterjee:: Ironmaking and steelmaking

Zhang and Fruehan: Metallurgical and Materials Trans. B, 26(8), 1995