Introduction to Slag Fundamentals

by

Eugene Pretorius
Process Technology Group LWB Refractories
a) What is slag?

Dictionary Definition:
"The dross or scoria of a metal" or "fused refuse separated from metal in smelting" - This
definition applies to smelting operations and primary steelmaking operations (blast furnace or
ferrochrome smelting). In the blast furnace slag originates from the gangue in the ore, ash in the
coal, and the fluxes (lime, doloma, Al2O3) that were added to melt the gangue and coal ash so
that the slag can be tapped from the blast furnace.

Preferred Definition:
Slags are ionic solutions consisting of molten metal oxides and flourides that float on top of the
steel (completely liquid or partially liquid). A partially liquid slag consists of a liquid fraction
and a solid fraction. As the solid fraction of the slag increases the fluidity of the slag decreases
and it changes from "creamy" to "fluffy", and eventually to "crusty" or solid.

Why know more about slags?

The drive in recent years by the iron and steelmaking industry to cut costs and still produce high
quality steels has illuminated the importance of good slag practices in primary and secondary
steelmaking processes.

There has been a gradual realization that the slag phase in steelmaking is not a necessary evil but
a crucial part of modern steelmaking practices. Neither goal of producing high quality steel nor
low costs can be realized by poor slag practices. The concept of "slag engineering" or "slag
optimization" is becoming more common in many steelmaking works, as the need to implement
these concepts are driven by more stringent steel quality requirements.

Despite the large volume of literature that has become available in recent years on slag-metal-
refractory interactions, the fundamentals of slag engineering or optimization is still poorly
understood and is still viewed by many as an art rather than a science.

This document will attempt to illustrate the fundamentals of slags and their impact on steel
quality and refractory wear, in a practical and easy to understand manner.

b) The function of slag in Steelmaking:

1. Cover the arcs in the EAF and LF and protect the refractories from arc-flare
2. Improve the quality of the steel by absorbing deoxidation products (SiO2, Al2O3) and
inclusions (clean the steel)
3. Dephosphorize in the furnace and desulfurize in the ladle
4. Protect the metal from oxidation
5. Protect the metal from nitrogen and hydrogen absorption
6. Insulate the steel to minimize heat loss
7. Be fully compatible with the refractory lining

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A "bad" slag will:

Do nothing to improve the quality of the steel

Be incompatible with the refractory container and dissolve it to satisfy its solution
requirements.
A "bad" ladle slag contain a large proportion of reducible oxides (FeO and MnO) that will
react with the steel to cause Al, Si, and Mn fading

The viscosity (or fluidity) of the slag is also an important property. However, here there are
somewhat conflicting requirements. A good slag for the metallurgical practice should have a
high fluidity (low viscosity), whereas, a good slag in terms of refractory wear should have a low
fluidity (high viscosity) to insure minimum penetration and reaction, and good coating
formation. A compromise is therefore required, i.e., a slag that is still fluid enough to refine the
metal but not to fluid to cause accelerated wear on the refractory, i.e., slags with a "creamy"
consistency. A creamy slag has the consistency of latex paint.

c) Where does slag come and how is the slag formed - The building blocks of slag

The composition of a slag is usually expressed in terms of the component oxides (or flourides)
on a weight percent basis. For example a slag could have the following composition:

wt% CaO 55
wt% SiO2 20
wt% MgO 8
wt% Al2O3 12
wt% CaF2 5

Where do these components come from?

CaO - Lime (98 % CaO)

- Dolomite (58 % CaO & 39 % MgO)
- Ca-Aluminate (45% CaO & 53% Al2O3)
- Refractories (dolomite)

MgO - Dolomite (58 % CaO & 39 % MgO)

- Magnesia (> 92% MgO)
- Refractories (Mag-C & Dolomite)

SiO2 - Oxidation of the Si in the scrap (Si + O2 = SiO2)

- Steel deoxidation (2O + Si = SiO2)
- Sand and dirt
- Refractories (High Alumina)

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Al2O3 - Oxidation of the Al in the scrap (2Al +3/2O2 = Al2O3)
- Steel deoxidation (3O + 2Al = Al2O3)
- Ca-Aluminate (45% CaO & 53% Al2O3)
- Bauxite (>80% Al2O3)
- Refractories (High Al2O3 sidewalls & bottoms)

FeO - Scrap (2Fe + O2 = 2FeO)

MnO - Scrap (2Mn + O2 = 2MnO)

- Steel deoxidation (O + Mn = MnO)

CaF2 - Fluorspar (90% CaF2)

d) Slag calculation example

How to calculate a slag composition in a ladle using a mass-balance approach

Consider the following additions to a ladle:

Amount % CaO % MgO % Al2O3

Lime 700 100
Dolomite 500 60 40
Ca-Aluminate 500 45 55
Al (100%) 340

Assumptions: No furnace slag was carried over into the ladle

The recovery of Al in the steel was 25%
(conversion factor for Al to Al2O3 is 1.89)

The mass-balance approach is used to calculate contributions of the various components.

CaO Contributions
Lime: 700 x 1 = 700
Dolomite: 500 x 0.6 = 300
Ca-Aluminate: 500 x 0.45 = 225
1225
MgO Contributions
Dolomite: 500 x 0.4 = 200

Al2O3 Contributions
Ca-Aluminate: 500 x 0.55 = 275
Steel deoxidation 340 x 0.75 x 1.89 = 485
760

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Total Slag Amount: 1225 + 200 + 760 = 2185
% CaO = 1225/2185 x 100 = 56.1
% MgO = 200/2185 x 100 = 9.1
% Al2O3 = 760/2185 x 100 = 34.8

e) Slag basicity and optical basicity

One of the formulations that had always eluded scientists and engineers was finding a universal
compositional parameter that can be applied to slag in a fashion similar to which the pH
formulation has been applied to aqueous solutions.

Slag component oxides can be classified as acidic, basic, or amphoteric (can act as an base or
acid). However, the physical measurement of the basicity of an industrial slag is still not
possible, even in these modern times. A number of formulations have been used to express the
basicity of a slag. The most common approach is the use of a basicity index in which the basic
oxides are placed on the numerator and the acid oxides on the denominator. Of these, by far the
most commonly used is the V ratio (%CaO/%SiO2). While this is useful as a first
approximation, in slags containing appreciable quantities of oxides other than CaO and SiO2 it is
%CaO + %MgO
a very imperfect expression of basicity. Other formulations such as %SiO2 or
%CaO + %MgO
%SiO2 + %Al2O3, and many more, are also sometimes used. The first problem with these
expressions is that they involve an arbitrary decision as to whether a component is basic or acidic
and does not incorporate the differences in the relative basicities (acidities) of the different
oxides. A second problem with these ratios is that the assessment of basicity becomes
impossible in slags free of any recognized acid component. However, the following two basicity
formulations are still commonly utilized to define oxidized slags (EAF or BOF) and reduced
slags (ladle or AOD reduction slags), respectively:

Basicity Index for oxidized slags (B3)

%CaO
B3 = %SiO + %Al O
2 2 3

Basicity Index for reduced slags (B5)

% Total basic components %CaO + %MgO
B5 = % Total acidic components = %SiO + %Al O + %CaF
2 2 3 2

It is common to also add FeO and MnO to the acidic components in the B5 ratio, provided that
their sum (FeO + MnO) is less than 5%.

Recently, a more fundamental indicator of slag basicity, namely optical basicity, has been
established. Using experimentally determined spectrographic information on a large number of
glasses and Pauling's electronegativity data, the optical basicity for many components could be
calculated. Table 1 shows optical basicity () values for the most common ladle slag
components.

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 Table 1. Values of optical basicity () of slag components.

Oxide Optical Basicity ()

Na2O 1.15
CaO 1.0
MgO 0.78
CaF2 0.67
TiO2 0.61
Al2O3 0.61
MnO 0.59
Cr2O3 0.55
FeO 0.51
Fe2O3 0.48
SiO2 0.48

The average optical basicity () for a slag of any composition can be calculated by means of the
expression:
= XAoxAOx + XBOyBOy + ... (1)
where,

mole fraction of component * number of oxygen atoms in oxide molecule (2)

X = mole fraction of component * number of oxygens in oxide molecule of all components

Thus, in a CaO-Al2O3-SiO2 slag for example:

NCaO
XCaO = N + 3N
CaO Al2O3 + 2NSiO2

3NAl2O3
XAl2O3 = N
CaO + 3NAl2O3 + 2NSiO2

2NSiO2
XSiO2 = N
CaO + 3NAl2O3 + 2NSiO2

The optical basicity concept has been used with great success in correlation with sulfide and
phosphorous capacities, as will be illustrated later.

While the optical basicity is currently the best compositional parameter available that can be
used to describe the composition (basicity) of a slag, it does not say anything about the physical
properties of a slag. For example, consider the following "slag" composition:

% CaO 62
% MgO 8
% SiO2 30

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The optical basicity of this slag can be calculated as = 0.756, which could be considered
sufficiently basic to ensure good sulfur removal and minimum refractory wear. However, the
calculation of this number is meaningless because the slag listed above is completely solid at
steelmaking temperatures, and it will only start to melt at 1790C and will be fully molten at
1950C.

The application of the optical basicity concept to steelmaking slags is only useful if the slags are
completely melted.

From the above illustration it is clear that significantly more information, such as solidus and
liquidus phase relations and viscosity data, are required in order to completely evaluate slags that
would be suitable in, for example, the ladle furnace.

f) The fluxing effect and the concepts of solidus and liquidus temperatures

Slags typically consist of the following oxide components: SiO2, CaO, MgO, Al2O3, FeO, MnO
and Cr2O3. The pure individual component oxides melt at very high temperatures as shown in
Table 2. Pure elements or oxides will melt at a specific temperature (Table 2). For example,
pure MgO will go from all solid at 2799C to all liquid above 2800C. In this case the solidus
temperature (where the material starts to melt) = liquidus temperature (where the material is fully
molten).

Table 2. Melting points of the pure component oxides.

Oxide Melting point (C) Melting point (F)

SiO2 1720 3128
CaO 2600 4712
MgO 2800 5072
Al2O3 2030 3686
FeO 1370 2498
MnO 1850 3362
Cr2O3 2260 4100
CaF2 1420 2588

Slags typically consist of a solution (mixture) of more than one oxide. For example, a pure CaO
"slag" will be completely solid at steelmaking temperatures and will only form a liquid slag at
temperatures above 2600C (4712F).

What is fluxing: When we add pure B to pure A and the addition of B to A results in a lowering
of the melting point of A we can say that B is fluxing A. Take salt for example: Salt is a flux for
ice we add salt on ice (or snow) to lower the melting point of the ice. Ice is also a flux for salt
ice will lower the melting point of salt. The resultant liquid (or slush) that forms when we add
salt to ice, or ice to salt, is a solution (mixture of salt and water). The same principle applies to
steelmaking for example a solution of SiO2, MgO, and CaO is called a slag.

It can be inferred that the extent of fluxing will be dependent on the amount of flux added.
Adding only a few grains of salt to a large chunk of ice will result in only a small amount of

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liquid (solution) formation and a remaining large chunk of ice. It is important to note that the
moment we have a solution or mixture then the solidus temperature liquidus temperature.

The solidus temperature is defined as the temperature where the first drop of liquid will start to
form and the liquidus temperature is the temperature where the mixture is completely molten.

From the above discussion it clear that extensive "fluxing" between the component oxides had to
occur at steelmaking temperatures in order to form liquid slags. The extent of fluxing between
the various oxides is usually shown graphically on phase diagrams. A phase diagram is really a
plot showing the fluxing effect of one oxide on another as a function of temperature and
composition. For example from the phase diagram of the components CaO and SiO2 it can be
determined exactly how much SiO2 must be added to CaO to have a completely liquid slag
(solution) at 1600C (2912F).

g) The slag balance

The approach that will be used to demonstrate slag principles is very simple. The slag
components are divided into two groups as follows:

Refractory Oxides Fluxing Oxides

CaO SiO2
MgO Al2O3
CaF2
Iron oxide

The individual components CaO (2600C) and MgO (2800C) are very refractory, but even
when these components are combined, minimal fluxing occurs between them and a liquid phase
will only form above 2300C (4712F). It is therefor common to find that dolomite, (~58% CaO
and ~39% MgO) as a refractory material in the steel industry.

The addition of other fluxes (component oxides or flourides) to CaO and MgO is therefore
required to form a liquid slag at steelmaking temperatures.

In very simple terms slag engineering can be defined as the balance between the refractory
oxides (CaO and MgO) and the fluxing oxides (SiO2, Al2O3, CaF2, and iron oxide). This balance
is typically expressed as a basicity ratio:

Refractory Oxides %CaO + %MgO

B5 = Fluxing Oxides = %SiO + %Al O + %CaF + FeO
2 2 3 2

The following simple set of figures give a graphical view of the balance between the refractory
oxides and the fluxing oxides.

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 A balanced slag ("creamy") -
Ideal for refractory protection and metallurgical requirements

Refractory Oxides Fluxing Oxides

(CaO & MgO) (SiO2, Al2O3, CaF2)

The addition of too much CaO and MgO -

Slag too stiff or solid - little metallurgical benefit. Little or no refractory protection

Fluxing Oxides

Refractory Oxides

The addition of too little CaO and MgO -

Slag too fluid - little metallurgical benefit, very aggressive toward refractory

Refractory Oxides

Fluxing Oxides

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As a general guideline a minimum B5 basicity ratio of 1.5 is required (60% refractory oxides
and 40% fluxing oxides) to obtain a reasonable ladle slag. However, while a B5 ratio of 1.5
might be adequate for silicate slags, it will be too low for slags containing considerable amounts
of Al2O3 and CaF2. The solubility of CaO in the slag increases as the Al2O3 contents of the slag
increases. In order to maintain a slag with a "creamy" consistency, greater amounts of lime must
therefore be added. The B5 basicity ratio for an aluminate slag (~ 25% Al2O3) is around 1.8.
When the slag contains considerable amounts of fluorspar, the required B5 basicity ratio could
be around 2.0 since fluorspar will increase the solubility of CaO and MgO in the slag.

From the above discussions it became clear that SiO2, Al2O3, and CaF2 are the three main fluxing
components in ladle refining operations. The fluxing potential of these components are not
equal!. SiO2 is the "weakest" flux to bring CaO into solution, whereas CaF2 is the most potent
flux to bring CaO into solution. One important point to note; if compared on a two component
basis; CaO-SiO2 , CaO-Al2O3, or CaO-CaF2, there is not much difference in the amount of CaO
the different fluxes can dissolve at a specific temperature. However, when the fluxes are
combined (SiO2 + Al2O3 or SiO2 + CaF2), the solubility of CaO in the slag increases
dramatically.

h) What are slag requirements?

To improve the quality of the steel!

To be compatible with the refractories!

These are not opposing goals! Since a basic slag practice is utilized for most grades of steel, the
best slag for steelmaking quality will also be the best slag for refractory compatibility. These
optimum slags have a "creamy" consistency and are normally just saturated with respect to CaO,
or MgO, or both. Slags can be classified as follows:

Slag Classification:

Crusty - Too much CaO (and/or MgO)

Fluffy - CaO/MgO saturated, Ok for refractories but not optimum for desulfurization

Creamy - Just CaO/MgO saturated, Good for steelmaking and refractories (Ideal)

Watery - Too liquid, aggressive to the refractories

The following simplified phase diagram of the CaO-Al2O3 system can be used to classify the
consistency (viscosity) of slags:

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 2600
(a) - Crusty (25% L, 75% CaO)
(b) - Fluffy (72% L, 28% CaO)
Temperature C (c) - Creamy (98% L, 2% CaO)
(d) - Watery (100% L)

2030
(a) (b) (c) (d)
Liquid (L)
CaO + L
Al2O3 + L

1400

CaO Al2O3
Figure 1. Utilizing a simplified phase diagram of the system
CaO-Al2O3 to classify slag consistency

In this discussion on slag fundamentals only the major slag components (CaO, MgO, SiO2,
Al2O3, CaF2, and FeO) will be considered. There are many other minor components such as
Cr2O3, MnO, TiO2, and P2O5, which have also an impact on the phase relations of slags. The
discussion of these components falls outside the realm of this paper on slag fundamentals.
Fortunately, the levels of these components are not very high (< 5%) in typical steelmaking
slags. Furthermore, the effect of some of these components on the phase relations is so similar
that they can be considered equivalent. A good example is FeO and MnO that behaves almost
identically in slags. The only difference is that slags involving FeO will be much lower melting
than slags involving MnO.

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LWB Refractories 12 Process Technology Group
 UTILIZING PHASE DIAGRAMS TO
DEMONSTRATE SLAG PRINCIPLES

by

Eugene Pretorius
Process Technology Group LWB Refractories

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1. Introduction
"Phase diagrams are the most useful tools a metallurgist can have for understanding slag-
refractory interactions"
These diagrams have been available in the literature for at least 30 years but very few people
have applied them to steelmaking slags. Most people never understood them and many used the
excuse that these diagrams depict equilibrium conditions, which were never attained under
steelmaking conditions, concluding that the diagrams were useless. However, in the ladle furnace
or stainless steel vessel, where the kinetics of the various reactions has been greatly enhanced,
(due to higher temperatures, extensive stirring and arcing) equilibrium conditions are now more
closely approached. The application of phase diagrams to slags can therefore be an extremely
useful tool to determine to optimum target slag compositions. Most steelmaking slags typically
consist of four or more components and are therefore difficult to visualize and almost impossible
to present in two dimensions on a piece of paper. However, the binary, ternary and quaternary
diagrams can still be utilized to demonstrate slag fundamentals and the phase relations observed
there will also apply in the more complex systems.
In this discussion on slag fundamentals only the major slag components will be considered.
There are many other minor components such as Cr2O3, MnO, TiO2, and P2O5, which have also
an impact on the phase relations of slags. The discussion of these components falls outside the
realm of this paper on slag fundamentals. Fortunately, the levels of these components are not
very high (< 5%) in typical steelmaking slags. Furthermore, the effect of some of these
components on the phase relations is so similar that they can be considered equivalent. A good
example is FeO and MnO which behaves almost identical in slags. The only difference is that
slags involving FeO will be much lower melting than slags involving MnO.

2. Utlizing the CaO-MgO system to explain binary diagrams

From the melting points of pure MgO (2800C) or pure CaO (2600C) it is clear the individual
components would never form a liquid slag at steelmaking temperatures. Could MgO and CaO
be combined to form a liquid slag at steelmaking temperature? Figure 1 is simplified phase
diagram (ignoring solid solution) of the CaO-MgO system.
Before we start it is important to define a few terms first:
In this diagram the composition of the two components (CaO & MgO) is presented on the
abscissa (X-axis) and the temperature on the ordinate (Y-axis). The diagram consists of four
areas: All Liquid are, All solid area (Lime + Periclase), and two solid + liquid areas (Lime +
Liquid and Periclase + Liquid). The melting points of pure CaO and pure MgO is shown by
points [l] and [p], respectively. The addition of MgO to CaO causes the melting point of CaO to
be lowered from point [l] on the diagram (2570C) to point [f] on the diagram (2300C). This
curved line [l]-[f] is called the liquidus line (or liquidus curve). The liquidus temperature is the
temperature above which no crystals can exist. It is the locus of temperatures at which crystals
first begin to appear on cooling the slag under equilibrium conditions. In a similar fashion, the
addition of CaO to MgO causes the melting point of MgO to be lowered from point [p] on the
diagram (2800C) to point [f]. This curved line [p]-[f] is also a liquidus line. The horizontal line
[g]-[h] is very important and is called the solidus line (2300C). Below this line no liquid exists,
and any mixture of CaO and MgO will be completely solid.

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 X
3000
~2800C
(5072F)
2800 ~2570 (p)
(4658F)
2600 Liquid (a)
(l) (b)
Temperature (C)

Lime Periclase + Liquid

2400 (c)
+ Liquid (d) (e)
(g) (h)
(f) ~2300 (4712F)
2200

2000
Lime + Periclase

1800

CaO 10 20 30 40 50 60 70 80 90 MgO
Weight %

Figure 1. Simplified phase diagram of the CaO-MgO system

In order to demonstrate the fluxing of effect on this diagram, consider a mixture X containing
60% MgO and 40% CaO (dashed line on the diagram).

At 2600C (point (a))

At 2600C, a 60% MgO - 40% CaO (mixture X) is completely liquid (- point (a) falls in the
liquid area of the diagram).

Between 2540C (b) and 2300C

When the fully liquid mixture X is cooled from 2600C (a) it will intersect the periclase + liquid
liquidus curve at 2540C (b) . At this temperature periclase crystals start to precipitate from the
liquid. This temperature ( 2540C (b)) is therefore the liquidus temperature for mixture X. It is
clear from the diagram that there are an infinite number of liquidus temperatures for mixtures to
the left and right of mixture X; the liquidus temperature is dependent on the composition of the
mixture.

As mixture X is cooled below 2540C, periclase crystals continue to precipitate from the liquid
and the liquid composition follows the path b f. At 2300C (f) all the remaining liquid
crystallizes to from lime + periclase so that, at temperatures below 2300C, mixture X will be
completely solid. The solidus temperature for mixture X is therefore 2300C.
At 2350C (c)
At 2350C, mixture X consist of periclase + liquid; point (c) falls in the liquid + periclase area.
The composition of the liquid at point (d) and the composition of the periclase is at point (e). The

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periclase at point (e) is not pure but contains a small of amount CaO in solid solution. The
amounts of liquid and periclase can easily be determined with the use of the lever rule:

ce dc
% Liquid = x 100 = 61 % Periclase = x 100 = 39
de de

Although extensive fluxing between CaO and MgO occur (Figure 1), forming a slag containing
only these two components is not possible at steelmaking temperatures. The phase diagram of
the CaO-MgO system, however, shows why dolomite (mixture of CaO and MgO) is successfully
used as a refractory material (very high solidus temperature).

3. IMPORTANT BINARY DIAGRAMS

The system CaO-SiO2

Figure 2. Phase diagram of the CaO-SiO2 system

An enlargement of the circled area in Figure 2 is shown in Figure 3.

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 Liquidus Boundary

% CaO - 64
% CaO - 56
% SiO2 - 36 C 2S % SiO2 - 44
C/S = 1.8 + C/S = 1.3
L
L
1600C
2912F

1460C
CaO - Saturation
2660F
Refractory compatible (Creamy)

Figure 3. Enlarged area of the CaO-SiO2 system

This diagram has the following important features:

1. SiO2 is a good flux for CaO and liquid CaO-SiO2 slags can be achieved at steelmaking
temperatures.
2. The composition of the CaO-saturated liquid at 1600C is:
% CaO 56
% SiO2 44
3. The equilibrium CaO-saturation phase in contact with this liquid is Ca2SiO4, which has a
melting point of 2130 C.
4. The solidus temperature of this liquid is about 1462C.

This diagram shows the very small area of workable slags in this system. Slags with a basicity
ratio (C/S) > 1.8 will be completely solid at steelmaking temperatures. The lever rule can be used
to calculate the respective amounts of liquid and solid for the slag area shown.

100
% Liq
90
80
70
% Liquid

60
50
40
30
20
10
0
1.3 1.4 1.5 1.6 1.7 1.8

C/S Ratio
Figure 4. % Liquid as a function of basicity (CaO/SiO2) in the CaO-SiO2 system at 1600C

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 The system CaO-Al2O3

Melting Point
of pure CaO
Liquidus Boundary

Melting Point
of pure Al2O3

33 % CaO
67 % Al2O3
61 % CaO
39 % Al2O3
1600C
2912F

~1400C
~2552F

Figure 5. The CaO-Al2O3 system

The diagram shows that extensive fluxing occurs between CaO and Al2O3. This is contrast to the
MgO-Al2O3 system where a very stable high-melting spinel phase MgAl2O4 is formed. The
reason why CaO does not react with Al2O3 to form a spinel phase is that the Ca2+ cation is too
large (1.14 ) to fit into the spinel structure. Other divalent cations such as Mg2+ (0.86), and
Fe2+(0.92 ) are small enough to fit in the spinel structure and they all form intermediate phases
with the spinel structure in those systems.

This phase diagram is a very important for Al-killed steel and it is also the basis for Ca injection
to modify the Al2O3 inclusions in the steel to be liquid. The target slags ladle or stainless steel
converter slags would be at CaO saturation, which at 1600C is 61% CaO and 39% Al2O3. The
target composition of the modified inclusions are typically in the blue area indicated on the
diagram, and ideally at around 50% Al2O3 and 50% CaO. This is close to the composition of the
C12A7 phase on the diagram.

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 The system CaO-FeOx

Figure 6. The CaO-FeO and CaO-Fe2O3 systems

Iron oxide (FeO or Fe2O3) is an excellent flux for CaO as shown by the low-temperature
eutectics in the diagrams above. The solubility of CaO in iron oxide is high, about 50% CaO for
FeO and about 55% CaO for Fe2O3, at 1600C (2912F). The formation of very low-melting
liquids in these systems and the large solubility of CaO show why dolomite refractories are very
vulnerable to slags with high Iron oxide levels.

The system CaO-CaF2

The phase diagram of CaO-CaF2 system is shown in Figure 7.

This diagram shows a few very important features:

1. Pure CaF2 is liquid at steelmaking temperatures

2. An eutectic exists between CaO and CaF2 at 1360C (F), and the composition of the slag
at the eutectic is: 83% CaF2 and 17% CaO - Point (a) on the diagram

3. The solubility of CaO in CaF2 at 1600(2912F) is not very high and the composition of
the slag at CaO saturation is: 26.6% CaO and 73.4% CaF2 Point (b) on the diagram.
The solubility of CaO in pure CaF2 is much lower than SiO2, Al2O3, or FeO, as shown in
Table 1:

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 Figure 7. The CaO-CaF2 system

Table 1 Solubility limit of CaO in the following systems at 1600C (2912F)

System % CaO at saturation

CaO-SiO2 56
CaO-Al2O3 61
CaO-FeO 48
CaO-CaF2 26

Fluorspar is rarely added by itself to a slag but normally added in combination with lime (usually
premixed). Consider the amounts of liquid that will be present if the following CaO-CaF2
mixtures are heated to 1600C:

Table 2 Amounts of liquid and solid for different CaO-CaF2 mixtures at 1600C

Mixture Composition % Liquid % Solid

90% CaO 10% CaF2 14 86
80% CaO 20% CaF2 26 74
70% CaO 30% CaF2 40 60
60% CaO 40% CaF2 54 46

It is important to note that the composition of the liquid phase for all the mixtures does not
change (Point (b) in the figure above).

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From the evaluation of the CaO-CaF2 system the following question then arises: Why is
fluorspar so popular as a flux since the ability of CaF2 dissolve lime by itself is very limited?
What other components are needed in the slag together with CaF2 to affect an increase in CaO
solubility?

The evaluation of the CaO-CaF2-SiO2 system provides significant insight on the combined effect
of CaF2 and SiO2 to drastically increase the solubility of CaO in the slag.

The system MgO-SiO2

Mg2SiO4

Liquid composition on liquidus

boundary at 1600C

Figure 8a. Phase diagram of the MgO-SiO2 system

An enlargement of the circled area in Figure 8a is shown in Figure 8b.

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 Figure 8b. Enlarged Area of the MgO-SiO2 system

A noteworthy feature of this diagram is the high solubility of MgO (42%) in a pure silica slag at
1600C (2912F). Fortunately, steelmaking slags also contain significant amounts of CaO which
will decrease the solubility of MgO in the slag. The effect of CaO on the solubility of MgO is
discussed in the section on CaO-MgO-SiO2 system.

The system MgO-Al2O3

Figure 9. The MgO-Al2O3 system

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An important feature of this system is presence of the very stable spinel phase (MgAl2O4). The
spinel phase is very refractory and as a result the lowest melting liquid in the MgO-Al2O3 system
is at about 1950C (3542F). At steelmaking temperatures, any combination of MgO and Al2O3
will result in a completely solid slag.

The system MgO-FeOx

Figure 10. The MgO-FeO and MgO-Fe2O3 systems

The ionic radii of Mg2+ and Fe2+ are very similar and for that reason FeO and MgO forms a
complete solid solution over the whole composition range. This has a very important implication
in terms of refractory wear and it shows why magnesia-carbon is an excellent refractory in
contact with iron-oxide rich slags. At 1600C (2912F), MgO can absorb up to 75% FeO before
a liquid phase will form. MgO is effectively acting as a "sponge" to absorb the iron oxide. The
diagrams also show that the solubility of MgO in a pure FeO slag is about 10%. Typical furnace
and BOF slags, also contain other components such as CaO, SiO2 and Al2O3, which will have an
important effect on the solubility of MgO in the slag.

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 The system MgO-CaF2

1600

Temperature (C)
L
1500

1400

1353

1300
MgO 20 40 60 80 CaF2
Wt% CaF2

Figure 11. The MgO-CaF2 system

The inferred phase diagram of the MgO-CaF2 system is shown in the figure above. There is some
discrepancy in the literature on the exact location of the MgO-saturation boundary, so the
diagram was redrawn utilizing the data from a number of ternary diagram which were in
agreement on the position of the MgO saturation curves.

The solubility of MgO in CaF2 at 1600C is about 48 wt%. This is significantly higher than CaO
in the equivalent CaO-CaF2 system (26.6% CaO). The composition of the eutectic (12% MgO) is
similar to that of the CaO-CaF2 system (17% CaO).

4. Utilizing the CaO-MgO-SiO2 system to explain ternary systems

In order to evaluate the fluxing effect of SiO2 on CaO and MgO together, an equilateral triangle
with the three components on the corners of the triangle is usually drawn. A map of the phase
relations as a function of temperature and composition for any mixture inside this triangle, under
equilibrium conditions, is plotted in the phase diagram as shown in Figure 12.

This diagram is fairly complicated and can be intimidating to most novice users. The question
now arises how can this diagram be used as a tool for the steelmaker.

Most steelmaking operations are conducted around 1600C (2912F) so that this diagram can be
greatly simplified if the phase relations is examined only at this temperature. Figure 13
(isothermal section at 1600C) is a simplified version of the figure and is easier to understand.

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 Figure 12. The CaO-MgO-SiO2 system

SiO2
1600C (2912F) Isothermal Section
S = SiO2
10 90
M = MgO
M2S = Mg2SiO4 20 Z 80
Sea area (all liquid)
S+L
C2S = Ca2SiO4 30 Land area (all solid)
70
L = liquid
Swamp area (liquid + solid)
40 60

50 X 50
M 2S + L
Mg2SiO4
60 O 40
C 2S + L
Ca2SiO4 M+L M 2S + L + M
K
70 C 2S + L + M 30
Ca3SiO5
80 20
Y

90 10

CaO 10 20 30 40 50 60 70 80 90 MgO
Figure 13. The 1600C Isothermal section of the CaO-MgO-SiO2 system

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As indicated in the legend, this diagram contains three distinct areas, which, for the sake of
simplicity have been labeled as follows:

Sea area (all liquid)

Land area ( all solid)
Swamp area (liquid + solid) Note the abbreviations used for the solid phases.

Applying the Lever Rule in the CaO-MgO-SiO2 system

The lever rule can be applied to calculate the phase composition of slags that fall in two-phase or
three phase slags regions.

Consider slag Z that falls in the silica + liquid two-phase region:

This area of interest has been enlarged and is shown in the next figure.

n p

Figure 14. Enlarged view of the SiO2 + liquid area.

For any mixture that falls in the SiO2 + liquid "swamp" area, the composition of the silica is
always at the silica apex (pure silica) and the composition of the corresponding liquid will be
somewhere on the silica liquidus curve (n to p). The exact composition of the liquid is
determined by drawing a line from the silica apex of the diagram (S) through the composition of
the slag until it intersects the silica liquidus curve (n-p). For mixture Z the point of intersection
is at (L). The composition of the liquid (L) can be read directly from the diagram. (%SiO2 =
67.4, %CaO = 16.3, %MgO = 16.3).

The relative amounts of liquid and silica can easily be calculated using the lever rule:

ZS ZL
% Liquid = x 100 = 61.2 % Silica = x 100 = 38.8
LS LS

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It is clear that if the composition of the slag is close to the silica apex then the amount of silica in
the slag will be large and the amount of liquid will be small, conversely, if the composition of
the slag is closer the silica liquidus curve the amount of liquid will increase.

Slag K falls in swamp area L + M + C2S. Because there are three phases* (2 solids + a liquid)
present, the compositions of all the phases are fixed so that this swamp area is defined by the
triangle C2S - liquid - M. The next figure is an enlarged drawing of the triangle joining the
compositions of these three phases.

M' C 2 S'

C 2S

L'

Figure 15. Enlarged view of the C2S + liquid + M "swamp" area.

Very Important: the composition of the liquid is fixed at point L (%SiO2 = 38, %CaO = 45,
%MgO = 17) which means that for any slag that falls within this triangle the composition of the
liquid portion of the slags stays constant but the relative amounts of the phases will change. The
relative amounts of the phases present in slag K can easily be calculated by drawing lines from
the apex's of the triangle through the slag composition point K until the triangle sides are
intersected.

KL' KC2S' KM'

% Liquid = x 100 % Ca2SiO4 = x 100 % MgO = x 100
LL' C2SC2S' MM'

% Liquid = 56.4, % Ca2SiO4 = 38.4, % MgO = 5.2.

The following figure show the slag composition paths of slag Y reacting with various
components and refractories

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 SiO2
1600C Isothermal Section
10 90
Liquid
20 80
Solid S+L

Liquid + solid 30 70

40 60

Slag Y
50 50
M2S + L
C2S + L M 2S
t S
60 L 40
C 2S O x M2S + L + M
70 s2 30
C2S + L + M
80 20

90 10

CaO 10 F 20 30 D 40 50 60 R 70 80 90 MgO
flux1 Dolomite Refractory

Slag Y reacting with dolomite refractory:

Slag Y dissolves refractory until saturated with MgO at S. The liquid composition moves from Y to S.
Liquids composition then follows liquidus curve S-O until CaO saturated. Overall solid composition
moves to S2 where reaction ceases.
Note that saturation for an MgO-C or periclase refractory is achieved when reaching the MgO + L or M2S
+ L phase boundaries

Figure 16. Slag Y reacting with materials of different chemistries

5. Important Ternary Systems

THE SYSTEM CAO-MGO-AL2O3

The liquidus surface for the CaO-MgO-Al2O3 system is shown in Figure 17 and the 1600C
(2912F) isothermal section for the system is shown in Figure 18.

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 Figure 17. The CaO-MgO-Al2O3 system

(a)

(b)

Figure 18. The isothermal section of the CaO-MgO-Al2O3 system at 1600C (2912F)
The system CaO-Al2O3-SiO2

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The liquidus surface for the CaO-Al2O3-SiO2 system is shown below:

Figure 19. The CaO-Al2O3-SiO2 system

The 1600C (2912F) isothermal section of the system is shown in Figure 20.

The solubility of CaO is plotted as a function of the Al2O3/(Al2O3+SiO2) ratio in the slag in
Figure 21. It effectively show the effect on the solubility of CaO as Al2O3 is replacing SiO2 in
the slag. This figure shows that in the CaO-Al2O3-SiO2 system, the replacement of SiO2 with
Al2O3 will initially result in a decrease in CaO solubility. However, a large increase in CaO
solubility only occurs when the Al2O3 content of the slag exceeds about 25% Al2O3 and the SiO2
content of the slag decreases from about 23% to 10% SiO2.

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 Figure 20. The 1600C Isothermal section through the CaO-Al2O3-SiO2 system
64
% CaO - 62.2
% SiO2 - 9.6
% Al2O3 - 28.3
62

60
0% SiO2
% CaO at saturation

0% Al2O3
58

56

% CaO - 50.3
% SiO2 - 23.2
54
% Al2O3 - 26.5

52

50
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Al2O3/(SiO2+Al2O3)

Figure 21. The CaO content at saturation as Al2O3 is replacing SiO2 in the slag

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Figure 21 clearly shows the interdependence of the CaO solubility on the SiO2 and Al2O3 levels
of the slag. The impact of these relationships is very significant on stainless steel production. In
stainless steelmaking the Al2O3 in slag is generated by the partial replacement of FeSi by Al as a
reductant, or FeSi containing high levels of Al. It is therefore very important to do an accurate
mass-balance calculation to ensure proper Al/Si reductant ratios in order to achieve the target
fluidity and desired CaO solubility.

The system MgO-Al2O3-SiO2

The liquidus surface of the MgO-Al2O3-SiO2 system is shown below:

Figure 22. The MgO-Al2O3-SiO2 system

The 1600C (2912F) isothermal section of the system is shown below:

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 Figure 23. The 1600C Isothermal section through the MgO-Al2O3-SiO2 system

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IMPORTANT METALLURGICAL SLAGS

1. Blast Furnace Slags

The following slag characteristics are important for maximum efficiency in operation of a blast
furnace:
1. The slag should be completely liquid at steelmaking temperatures.
2. The slag should be such that uncontrollable variation in its composition is tolerated without a
troublesome slag developing.
3. The slag should have high sulphur removing capacity
4. The slag should have favourable flow and diffusion characteristics (low viscosity)
An excellent starting point for an evaluation of optimum slag composition in terms of the above
criteria is afforded by phase equilibria at liquidus temperatures in the system CaO-MgO-Al2O3-
SiO2. For the purpose of the present discussion a plane of constant Al2O3 content (10%) will be
used as an example for more detailed discussion. It is seen in Figure 8.1 that the liquidus surface
is very steep and liquidus temperatures in general are high in the primary phase areas of
periclase, lime, tri-and dicalcium silicate, forsterite, and silica, whereas the liquidus surface is
relatively flat and liquidus temperatures are relatively low in the primary phase areas of
pseudowollastonite, pyroxene, melilite, merwinite and monticellite.

Figure 1. Phase relations at liquidus temperatures in the 10% plane of the

system CaO-MgO-Al2O3-SiO2. Mer = merwinite, Mon = monticellite.

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The performance of slags within this plane in terms of the four criteria listed above at the
temperature of 1500 will be considered in the following. First, mixtures within the area bound
by the 1500C liquidus isotherm in Figure 1 are all liquid at the temperature under consideration
and hence meet requirement (1). For the sake of clarity, this area has been crosshatched in the
simplified diagram of the 10% Al2O3 plane shown in Figure 2.

The second requirement, that of latitude with respect to possible uncontrollable composition
changes, makes it desirable to avoid close approach to composition areas where a crystalline
phase starts to separate out, viz., the outline of the shaded area.

The situation with respect to the third requirement, that of high sulphur-removing capacity may
be evaluated approximately from thermodynamic data for pure oxide and sulphide components.
The sulphur-removing capacity of the slag components in the system of interest increases in the
order SiO2 < Al2O3 < MgO < CaO. Clearly, low SiO2 (and Al2O3) content and high CaO (and
MgO) content are desired in order to achieve the best possible sulphur retention by the slag. The
critical question is: For the given alumina content of 10%, what is the lowest possible silica
content?

Figure 2. Simplified diagram showing phase relations in the 10% Al2O3 plane through the
system CaO-MgO-Al2O3-SiO2 at 1500C

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From the diagram in Figure 2 it is seen that the minimum silica content within the all-liquid
region is that at point a ( 32% SiO2, 44% CaO, 14% MgO), representing a liquid in
equilibrium with merwinite and periclase. Attempts to decrease the SiO2 content below this
value, at 1500C, would only result in precipitation of merwinite and/or periclase crystals
without changing the SiO2 content of the liquid significantly. Hence a liquid of composition
represented by point a is inferred to have the highest sulphur removing capacity a the chosen
level of Al2O3 content.

The fourth requirement listed, that of low viscosity, very conveniently is fulfilled when the third
requirement is fulfilled. The viscosity of an alumino-silicate liquid is primarily a function of the
degree of polymerisation of silicon-aluminium-oxygen tetrahedra. The "basic" oxides CaO and
MgO help to break up the links among the tetrahedra in these polymerised structures, and
promote the tendency for formation of isolated tetrahedra. Hence the viscosity of the liquids
decrease with increasing content of CaO and MgO. For a given Al2O3 content, therefore, the
viscosity of the liquid phase will be lower the lower the SiO2 content is. There is a limit for this
tendency, however. At very low SiO2 contents (below that of point a in Figure 2) the viscosity
starts to increase with decreasing SiO2 content because increasing amounts of crystals are
suspended in the liquid. The minimum viscosity therefore is reached for the liquid represented
by the point of lowest silica content a within the all-liquid area.

2. BOF and EAF Slags

Virtually all modern steelmaking slags are to be found in the CaO-SiO2-FeO "ternary" system
(Figure 3). The 1600C isothermal section through this system, in contact with metallic iron, is
shown in Figure 4. The crosshatched area in this figure comprises compositions of mixtures
which were all liquid at 1600C. This system (Figure 4) is dominated by four characteristics:
the high melting point of CaO (2572C), the presence of dicalcium-silicate (Ca2SiO4) which is
very stable and which also has a high melting point (2130), the miscibility gap in the liquid field
near the silica apex of the system, and the relatively low melting point of iron oxide (1365C).
For maximum desulphurization and dephosphorization capacity of the slags, it is important to
obtain homogeneous liquids with the lowest possible SiO2 contents which are simultaneously as
close as possible to being saturated with CaO at steelmaking temperatures. Hence the region of
the diagram separating the all-liquid area from those where liquids coexist in equilibrium with
either CaO or the calcium silicates (Ca3SiO5 and Ca2SiO4) are particularly important in
steelmaking technology.
Magnesia (MgO) is another important ingredient of steelmaking slags, which needs to be
saturated with MgO to minimize slag attack on the magnesia refractory lining of the
vessel/furnace. The effect of MgO on the solubility of calcium silicates and calcium oxide is
shown in Figure 5 for the system CaO-MgO-FeO-SiO2, in equilibrium with metallic iron at
1600C. Note how with increasing MgO levels the stability field of C2S is depressed.

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 Figure 8.3. Phase relation in the system CaO-SiO2-FeO in contact with metallic iron.

Figure 8.4. The 1600C isothermal section through the system CaO-SiO2-FeO.

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 Figure 5. Effect of MgO on the solubility isotherms at 1600C in the system CaO-MgO-FeO-
SiO2 in contact with metallic iron

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