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The Effect of Fluorspar in Steelmaking slags

By
Eugene Pretorius
Baker Refractories
Epretorius@bakerref.com

Introduction
Fluorspar (CaF2) is probably the "black sheep" of the steelmaking industry and has been
blamed for more refractory slagline failures than anything else. For this reason CaF2 is
considered evil and the use of CaF2 has been banned in many shops. In this section the
effect of fluorspar on steelmaking slags and refractories will be evaluated in a practical
and scientific manner, and hopefully it will dispel some of the myths regarding this
component. It will show the considerable advantages of using fluorspar in steelmaking
slags, but it will also show the possible devastating effect on refractories if fluorspar is
used inappropriately. This paper will not address any of the environmental concerns
regarding the use of fluorspar but will only focus on the technical aspects of this
component in steelmaking.
Fluorspar as desulfurizing agent
One of the biggest misconceptions in the steelmaking industry is that fluorspar will
desulfurize the steel. It is not fluorspar but dissolved lime in the slag that is responsible
for desulfurization. The amount of CaO that can be dissolved in a slag is a function of
slag composition and temperature. Once the CaO-saturation point of a slag is reached,
any further addition of lime to the slag will only increase the viscosity of the slag (further
precipitation of CaO or CaO-rich phases), and will inhibit desulfurization.
The addition of fluorspar to some slags will increase the solubility of CaO and thus give
the slags greater desulfurization potential. It is this increased CaO solubility (assuming
that the lime is added) that increases the sulfide capacity of the slag, which results in
improved desulfurization. The addition of CaF2 to a fully liquid slag, without adding
lime to maintain CaO-saturation, will do nothing for desulfurization but drastically
increase refractory wear. Unfortunately, it is common to find operators adding fluorspar
to a liquid slag, without additional lime, in an attempt to lower the sulfur content of the
steel.
The component fluorspar by itself is not a good desulfurizing component. This is
demonstrated in the following table that shows the optical basicity values for the most
common steelmaking components (higher optical basicity values are better for
desulfurization).
Table 1. Optical basicity values for typical slag components
Component
CaO
MgO
Al2O3
SiO2
CaF2

Optical Basicity Value ()


1.00
0.78
0.61
0.48
0.68

From this table it is clear that CaO in solution has the highest desulfurizing ability and
CaF2 is a distant third behind MgO. Even the combination of CaO and SiO2 (lowest
basicity) to form a CaO-saturated slag, will still desulfurize better than a pure CaF2 slag.
This is shown in the table below, where optical basicity, sulfide capacity correlations and
thermodynamic data were used to calculate the final sulfur in the steel. The following
parameters were considered in the calculation:
Temperature (C)
Slag Amount (kg)
Metal Amount (kg)
Initial Sulfur (%)
Oxygen Level in Steel (ppm)

1600
2000
100000
0.05
15

Table 2. Calculated slag and metal parameters for a CaO-saturated CaO-SiO2 slag
and a pure CaF2 slag at 1600C.
CaO-SiO2 Slag
56
44

% CaO
% SiO2
% CaF2
Optical Basicity
Sulfide Capacity
Sulfur Distribution Coeff.
Final Sulfur (%)

0.691
-3.119
13.82
0.0392

CaF2 Slag

100
0.680
-3.275
9.65
0.0419

Why is CaF2 added to a slag?


1) To increase the solubility of basic components (CaO & MgO) in the slag
2) To act as a fluxing precursor
3) To maintain fluidity in the slag as the slag temperatures decreases
CaF2 will increase the solubility of CaO in silicate slags and therefore increase the
effective sulfide capacity of the slag. In aluminate slags (> 25% Al2O3) the addition of
CaF2 does not increase the solubility of CaO in the slag. The effect of CaF2 in aluminate
slags will be discussed in detail later.
When should CaF2 be added to a slag.
The addition of CaF2 to a stiff silicate slag (CaO over-saturated) will increase the fluidity
of the slag as CaF2 will melt immediately at steelmaking temperatures. More
importantly, it will bring more CaO into solution. In contrast, the addition of CaF2 to a
stiff high-Alumina slag will only slightly increase the fluidity of the slag (liquid CaF2),
since CaF2 has a limited effect on the solubility of CaO in these slags.

Fluorspar should never be added in the stir-eye of a ladle, but instead to the bulk of the
slag (middle of the ladle). If the CaF2 is added in the stir-eye of a ladle, it will not only
dissolve the solid lime in the slag, but also dissolve the basic components of the slagline
refractories in the vicinity of the stir area. Unfortunately, CaF2 added in this fashion does
not discriminate between undissolved lime in the slag or CaO and MgO in the slagline
refractories. The addition of CaF2 in the stir-eye obviously results in a very liquid slag
with a very high CaF2 concentration locally. The chemical potency of this slag to
dissolve basic oxides and the turbulence of the stir-eye can lead to significant localized
refractory wear.
If CaF2 is used as a ladle slag additive, it is generally recommended to add CaF2 in a
premixed form together with lime and silica sand or Ca-Aluminate.
The phase relations of CaF2 with various oxides.
In order to understand the behavior of CaF2 in slags it is important to first evaluate the
binary phase relations of CaF2 with other components and then consider more
complicated higher order systems.
The system CaO-CaF2
The following figure shows the phase diagram of the CaO-CaF2 system.

Figure 1. Phase diagram of the CaO-CaF2 system

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 the next table:
Table 3. Solubility limit of CaO in the following systems at 1600C (2912F)
System
CaO-SiO2
CaO-Al2O3
CaO-FeO
CaO-CaF2

% CaO at saturation
56
61
48
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 4. Amounts of liquid and solid for different CaO-CaF2 mixtures at 1600C
Mixture Composition
90% CaO 10% CaF2
80% CaO 20% CaF2
70% CaO 30% CaF2
60% CaO 40% CaF2

% Liquid
14
26
40
54

% Solid
86
74
60
46

It is important to note that the composition of the liquid phase for all the mixtures does
not change (Point (b) in Figure 1).
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 (Figure 2) provides significant insight on
the combined effect of CaF2 and SiO2 to drastically increase the solubility of CaO in the
slag.

The CaO-CaF2-SiO2 system

Figure 2. Phase diagram of the CaO-CaF2-SiO2 system


The most striking feature of this diagram is the tremendous increase in the solubility of
CaO when CaF2 is added CaO-SiO2 slags or when SiO2 is added to CaO-CaF2 slags. The
combined effect of SiO2 and CaF2 results in a very high CaO solubility and the maximum
solubility at 1600C is shown by point (a) on the diagram. The composition of the slag at
this point is approximately the following:
% CaO 72
% SiO2 16
% CaF2 12
The CaO content (saturation) on the 1600C isotherm in Figure 2 was traced from the
CaO-SiO2 binary to the CaO-CaF2 binary system. This saturation solubility of CaO in
CaO-CaF2-SiO2 system is plotted as a function of the SiO2 content of the slag in Figure 3.

75
Slag (a) in Fig. 2

% CaO in Solution

70

65

60

55

50
10

15

20

25

30

35

40

% SiO2

Figure 3. Solubility of CaO as a function of SiO2 content in


CaO-CaF2-SiO2 slags at 1600C
The maximum in CaO solubility is at about 12% CaF2 in the slag. The addition of more
CaF2 to the slag, while still maintaining CaO saturation, results in a decrease in CaO
solubility. This is because the SiO2 content of the slag is diluted to below 18%. From
this it is clear that the maximum amount of fluorspar that would ever be required in a slag
is 12%. The addition of more CaF2 would either result in a decrease in CaO solubility or
an increase in fluidity that could lead to an increase in refractory erosion.
The diagrams shown above are especially useful in designing flux recipes for rapid liquid
formation. Consider the following mixtures in Table 5:
Table 5. The combined effect of SiO2 and CaF2 in the solubility of CaO at 1600C

% CaO
% SiO2
% CaF2
% Liquid
% Solid

Mixture 1
70
30

Mixture 2
70
30
40*
60

0
100

Mixture 3
70
15
15
100
0

*The composition of the liquid for mixture 2 only contain about 27% CaO in solution.

The combination of CaF2 and SiO2 in the right proportions can create slags in the CaOCaF2-SiO2 system with excellent desulfurization abilities as shown in the Table 6 below.
(Using the same parameters listed earlier)
Table 6. Calculated slag and metal parameters for CaO-saturated slags at 1600C.

% CaO
% SiO2
% CaF2
Optical Basicity
Sulfide Capacity
Sulfur Distribution Coeff.
Final Sulfur (%)

CaO-SiO2
Slag
56
44

CaO-CaF2
Slag
26.6
73.4
0.744
-2.345
82.2
0.0189

0.691
-3.119
13.8
0.0392

CaO-CaF2-SiO2 slag
(slag (a) Fig. 2)
72
16
12
0.823
-1.208
1127.1
0.0021

While the theoretical slags discussed above show tremendous potential in terms of
desulfurization, they are difficult to attain under real steelmaking conditions. The
principal reason is that most real steelmaking slags also contain the components MgO
and Al2O3, which will also influence the solubility of CaO. Most slagline refractories are
MgO based so that MgO saturation becomes an important requirement in steelmaking
slags. The effect of MgO on the solubility of CaO will be discussed later in more detail.
Although the theoretical slags of the CaO-CaF2-SiO2 system has limited applicability as
target slags for ladle applications, they are very important in terms of designing flux and
additions recipes. This system shows that CaF2-CaO-SiO2 mixtures have the potential to
go into solution much faster than CaF2-CaO mixtures. The phase diagram in Figure 2 also
shows that for slags containing SiO2 and CaF2 in approximately a 1:1 ratio is almost
parallel to the slopes of the liquidus lines in the diagram. This is a very important
observation and should be considered for flux recipes. Consider for example, mixtures 2
and 3 in Table 5. Mixture 3 could potentially melt completely if exposed to steelmaking
temperatures, whereas Mixture 2 would require SiO2 from another source (steel
deoxidation) to become fully liquid. This also shows that combining the CaF2 with
silica sand might minimize the amount of CaF2 added to a slag.
The addition of CaF2 to high-alumina slags
In the previous section on the CaO-SiO2-CaF2 system, a tremendous increase in the
solubility of CaO was demonstrated for slags containing a combination of SiO2 and CaF2.
The question arises whether the same fluxing effect will be present if CaF2 is combined
with Al2O3.
The following figure shows the isothermal section of the CaO-Al2O3-CaF2 system at
1600C.

Figure 4. Isothermal section through the CaO-Al2O3-CaF2 system at 1600C


From this figure, it is clear that CaF2 in combination with Al2O3 does not show that same
behavior as it does in combination with SiO2. The addition of Al2O3 to the CaF2-CaO
system does result in a significant increase in the solubility of CaO. However, the
addition of CaF2 to the CaO-Al2O3 system results in a decrease in the solubility of CaO.
It is therefore clear that CaF2 is not a good flux to increase the solubility of CaO in CaOAl2O3 slags. The replacement of Al2O3 with CaF2 results in a decrease in the solubility of
CaO as indicated by the two CaO-saturated slags in the following table:
Table 7. CaO-saturated slags in the CaO-Al2O3-CaF2 system at 1600C

% CaO
% Al2O3
% CaF2

Slag (a)
61
39

Slag (b)
50
30
20

Comparison to the CaO-Al2O3-SiO2 system


This section is mainly concerned with the effect of CaF2 on slags, but it is useful to
consider phase relations in the CaO-Al2O3-SiO2 system for comparison. Figure 5 shows
the isothermal section of the CaO-Al2O3-SiO2 system at 1600C.

Figure 5. Isothermal section through the CaO-Al2O3-SiO2 system at 1600C.


This diagram shows a few very important features:
1. The phase field of Ca2SiO4 is much larger in this system than the CaO-CaF2-SiO2
system indicating that CaF2 is more potent than Al2O3 to bring Ca2SiO4 into solution.
2. The addition of Al2O3 to CaO-SiO2 slags initially results in a decrease in CaO
solubility, but when the SiO2 content of the slag drops below about 20%, a significant
increase in CaO solubility is observed.
3. The addition of SiO2 to CaO-Al2O3 slags results in a very small increase in CaO
solubility, indicating SiO2 is actually a better flux than CaF2 in CaO-Al2O3 slags.
4. A maximum in the solubility of CaO on the CaO-saturated phase boundary is also
observed, similar to that in the CaO-CaF2-SiO2 system. However, this maximum
CaO solubility value in the Al2O3 system is significantly lower than the CaF2 system,
as indicated by the following table.
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Table 8. Maximum CaO solubility limits of slags in the CaO-CaF2-SiO2


and CaO-Al2O3-SiO2 systems.

% CaO
% SiO2
% CaF2
% Al2O3

CaO solubility maximum


in CaO-CaF2-SiO2 system
72
16
12

CaO solubility maximum


in CaO-Al2O3-SiO2 system
62
10
28

Based on the phase relations in the systems discussed so far, it is expected that slags in
the CaO-Al2O3-SiO2-CaF2 system will probably show similar phase relations as slags of
the system CaO-SiO2-CaF2. The ability of CaF2 to increase the solubility of CaO will be
probably be limited until the SiO2 content of the slag approaches about 15% SiO2.
The implication of the above to steelmaking practice is the following:
In high-Al2O3 slags with low SiO2 content (< 6% SiO2 - Al-killed grades where the Si
content of the steel is restricted), the addition of CaF2 to slag will probably not result in
an increase in the solubility of CaO in the slag (improve desulfurization). However, the
addition of CaF2 to these slags will probably result in a depression of the solidus
temperature of the slag (complete solidification at lower temperatures).
For the other grades of Al-killed steel or Al/Si-killed steel, the addition of CaF2 to highAl2O3 slags that contain appreciable amounts SiO2 (10-15%), might increase the
solubility of CaO significantly and hence improve desulfurization, or increase refractory
wear if not careful (catch 22).
The use of CaF2 as a fluxing precursor in high-Al2O3 slags.
For most Al-killed steel grades, the amount of slag carried over from an EAF or BOF to
the ladle is minimized. In some shops the slag is even raked off before further processing
at the ladle refining station. In these cases a new synthetic slag has to be made from
scratch. The volume of the new synthetic slag should be adequate to cover the steel and
stabilize the arcs at the ladle furnace. The following could be a typical target ladle slag
composition:
% CaO 55
% MgO 7
% Al2O3 25
% SiO2 - 13
There are a number of ways this composition can be attained in a ladle. The choice of
raw materials used will have a dramatic impact on the time it will take for the slag to be
fully liquid and homogeneous in the ladle. The advantages and disadvantages of the
different raw materials are summarized in the next table.

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Table 9. Advantages and disadvantages of different raw material additions


Raw Material
Residual
Carryover Slag
Prefused CaAluminate
Lime &
Dolimite
Bauxite (or
other highAl2O3 material)
Silica Sand
Fluorspar

Advantages
Very good fluxing precursor:
Liquid and hot. Its free.

Disadvantages
Could cause Si and P reversions.
Require slag deoxidants (CaC2, Al)
to reduce the FeO and MnO
Good fluxing precursor: Melts
Very expensive. (Check that the
immediately when heated to
composition is approximately 50%
steelmaking temperatures
CaO and 50% Al2O3)
Inexpensive. Required for steel
Very refractory at steelmaking
cleanliness and quality, and
temperatures. Need a fluxing
refractory compatibility
precursor to get it into solution
Relatively inexpensive compared Very refractory at steelmaking
to prefused Ca-Aluminate
temperatures. Need a fluxing
precursor to get it into solution
Inexpensive
Can not be used in steel with low
Si specifications
Good fluxing precursor: Melts
Could cause extensive refractory
immediately when heated to
damage if the amounts and method
steelmaking temperatures.
of addition is not controlled
Relatively inexpensive compared
to prefused Ca-Aluminate.

In most shops it is important to create a liquid and desulfurizing slag as soon as possible
in the ladle. In order to achieve this goal a certain amount of fluxing precursor is needed
in the ladle. The fluxing precursors are added to bring the bulk addition of lime and highAl2O3 materials into solution. The fluxing precursor will melt immediately when heated
to steelmaking temperatures and then provide the liquid medium into which the other
refractory components can be dissolved. The possible fluxing precursors are:
Residual Carryover slag

Prefused Ca-Aluminate

&

Fluorspar

It now becomes a choice between economics and steelmaking requirements. The


addition of large amounts of Ca-Aluminate could drastically decrease the time to make a
liquid slag and process the heat. However, the addition of more prefused Ca-aluminate
also greatly increases the cost of producing the steel. Residual carryover slag is also an
excellent fluxing precursor. However, the amount of carryover slag that can be tolerated
will depend on the grade of steel and the composition of the carryover slag. If P and Si
reversions are a concern, then the amount of carryover slag must be carefully controlled.
An obvious goal therefore would be to balance the amount of carryover slag with the
amount of Ca-aluminate added.
It is certainly possible to only use the refractory end-member components such as lime,
dolomite, bauxite (or another high Al2O3 material) and silica. All the components
individually are solid at steelmaking temperatures and if added together will have to react

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first to create intermediate liquid phases and eventually become a liquid slag. Slags
formed this way normally take a long time to become fully liquid and homogeneous (at
least 30 minutes of vigorous stirring and arcing). During this time little or no
desulfurization occurs due to the inhomogeneity of the slag and the limited amount of
CaO in solution.
In the discussion above the advantages and disadvantages of carryover slag and prefused
Ca-aluminate was illuminated. The question now arises whether flourspar could be
utilized as a fluxing precursor in order to decrease the dependence on prefused Caaluminate and/or carryover slag as fluxing precursors. In the discussion of the CaOAl2O3-CaF2 system it was shown that CaF2 does not increase the solubility of CaO.
However, fluorspar might be used as a fluxing precursor to enhance the kinetics of Al2O3
and CaO dissolution. The added fluorspar will melt immediately and provide the liquid
medium to enhance reaction between CaO and Al2O3. The next figure shows significant
fluxing of Al2O3 by CaF2 in the Al2O3-CaF2 system.

Figure 6. Phase diagram of the Al2O3-CaF2 system


The solubility of Al2O3 in CaF2 at 1600C is about 50% Al2O3 as shown by the small
circle in the figure. This high Al2O3 slag would then be very effective to bring the added
lime into solution. The partial replacement of some of the prefused Ca-aluminate with
fluorspar could drastically decrease flux cost and hence the cost per ton of steel produced.
However, when fluorspar is utilized considerable care should be taken to ensure CaO
and/or MgO saturation in the slag to minimize refractory wear.
To section above can be summarized as follows: The addition of CaF2 to high-alumina
slags will probably not increase the solubility of CaO and hence the sulfide capacity of
the slag. However, the addition of CaF2 as a fluxing precursor when the pure
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component end-members lime and bauxite are added to create a synthetic slag, might
improve the kinetics of slag formation, which in turn might improve the overall kinetics
of desulfurization. One major drawback on the use of CaF2 in these slags is that the
addition of CaF2 significantly increases the solubility of MgO in the slag (discussed in a
later section). Great care should be taken to ensure that the slag is either CaO or MgO
saturated, or both, in order to limit the extent of refractory wear.
The effect of CaF2 on Refractories.
The biggest reservation on the use of CaF2 in the steelmaking industry (besides
environmental concerns) has been the effect of fluorspar on refractory wear. In some
shops fluorspar has been used for many years without any negative effect in refractory
life, whereas in other shops, the introduction of fluorspar resulted in significant increased
refractory wear. The principal reason for increased refractory wear when using fluorspar
is the lack of CaO and/or MgO saturation in the slag. Fluorspar in combination with
silica is a very potent flux to bring basic oxides into solution. If fluorspar is added to a
slag without the matching basic oxide additions to maintain saturation, then dissolution of
the basic refractories will occur. It is not the presence of CaF2 that is causing refractory
wear but rather the lack of CaO (or MgO) saturation in the slag. In some cases the
misuses of spar; either added at the wrong time or for the wrong reason will also
contribute to increased refractory wear.
The effect of CaF2 on CaO-bonded refractories (dolomite)
In the previous discussion it was clearly shown that fluorspar in combination with SiO2 is
a very potent flux to bring CaO into solution. If lime is added to the slag until the slag is
CaO-saturated there will be minimal refractory wear on lime-bonded (dolomite)
refractories. However, if additional lime for saturation was not added, the presence of
fluorspar in the slag could lead to accelerated refractory wear. This slag will have a
lower viscosity, a lower solidus temperature and a high capacity to bring lime into
solution and will lead to a deeper slag penetration into the refractory and increased
refractory wear.
It is not the presence of CaF2 that is causing refractory wear in CaO-bonded refractories
but the lack of lime saturation. A very liquid silicate or aluminate slag that is CaO
unsaturated, and contains no CaF2, will also be very aggressive to the refractories.
The effect of CaF2 on magnesia refractories
Most slagline refractories are MgO based, so it important to evaluate the effect of CaF2
on the solubility of MgO. The inferred phase diagram of the MgO-CaF2 system is shown
in Figure 7. There is some discrepancy in the literature on the exact location of the MgOsaturation 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

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eutectic (12% MgO) is similar to that of the CaO-CaF2 system (17% CaO). The phase
diagram for the MgO-CaF2-SiO2 system is shown in Figure 8.

Temperature (C)

1600

1500

1400
1353

1300

MgO

20

40

60

80

CaF2

Wt% CaF2

Figure 7. Redrawn Phase diagram of the MgO-CaF2 system

Figure 8. Phase diagram of the MgO-CaF2-SiO2 system

15

From this figure it is clear that there is some discrepancy in the solubility of MgO in pure
CaF2 slags. This figure indicates about 62% MgO at 1600C whereas the binary system
MgO-CaF2 indicates about 48% MgO. Most other ternary diagrams indicate a MgO
solubility on the binary join of about 48% MgO. However, the important feature of this
diagram is the significant increase in the solubility of MgO when CaF2 is added to the
MgO-SiO2 system. If it is assumed that the MgO solubility is about 48% at 1600C on
the MgO-CaF2 join, and then the 1600C isotherm can be redrawn as follows:
40%
MgO

SiO2

CaF2
MgO

60%
CaF2

Figure 9. Isothermal section at 1600C in the MgO-CaF2-SiO2 system


in the proximity of the MgO apex.
The composition of the slag at the maximum MgO saturation point on the 1600C
isotherm is approximately:
% MgO 58
% SiO2 22
% CaF2 - 20
The inferred phase relations as shown by the preceding figures are similar to that
observed in the CaO-SiO2-CaF2 system. From these figures it is clear that CaF2 is also a
very potent flux for MgO. This means that considerable care should be used when using
CaF2-containing in slags in contact with MgO-based refractories. The saturation levels of
MgO in these slags are significantly higher when the slag contains CaF2 than when the
slag just contains SiO2 and/or Al2O3 as fluxing components.
Most of the discussions so far have centered on the phase relations of fluorspar with only
one or two components. The reason for this, is the phase diagrams for these systems are

16

available. The phase relations of fluorspar with multi-component slags, and typical
steelmaking slags, are not available. The relations observed in the simple systems have
to be extrapolated and approximated for the more complex systems.
Most basic steelmaking slags contain appreciable amounts of MgO and are mostly in
contact with magnesia-based refractories. It is therefore very important to approximate
the effect of fluorspar on the CaO and MgO phase boundaries in silicate and aluminate
slags.
The effect of MgO on CaO solubility
Before the effect of CaF2 on complex slags will be discussed it is important to evaluate
the effect of MgO on the solubility of CaO. A key slag requirement for compatibility
with magnesia-based slaglines is MgO saturation. A typical practical slag aim is dual
saturation with respect to CaO and MgO. These dual saturation slags always have the
lowest MgO solubility as shown in the next two figures.

Slags compatible
with Magnesia-C
refractories:
MgO-Saturated

SiO2
10

1600C (2912F) Isothermal Section


90

20

80

Sea area (all liquid)

S+L
30

Land area (all solid)

70

Swamp area (liquid + solid)

40

60
50

50
60
C2S + L
Ca2SiO4
70
Ca3SiO5
80
90

CaO

10

M2 S + L

Mg2SiO4
40

M2S + L + M

M+L

30

C 2S + L + M

Slags compatible with both


dolomite and Magnesia-C
refractories:
MgO
20
3and
0
4CaO-Saturated
0
70
50
60

20
10

80

90

MgO

Figure 10. The 1600C isothermal section for the CaO-MgO-SiO2 system

17

% MgO dissolved in the Slag

45

1700C
1600C

40
35

Slag P
30
25
20

Slag O
(Dual Saturated)

15
0.4

0.6

0.8

1.0

1.4

1.2

% CaO/% SiO2
Figure 11. The solubility of MgO as a function of slag basicity in the
CaO-MgO-SiO2 system.
The next table shows the decrease in CaO solubility when MgO is added to the CaO-SiO2
and CaO-Al2O3 binary systems until dual saturation is achieved:
Table 10. The effect of MgO on the solubility of CaO at 1600C

Saturation
% CaO
% MgO
% SiO2
% Al2O3

CaO-SiO2
CaO Saturation
56
44

CaO-MgO-SiO2
Dual Saturation
44
17
39

CaO-Al2O3
CaO Saturation
61

CaO-MgO-Al2O3
Dual Saturation
53
10

39

37

While dual saturation (CaO and MgO) is recommended for magnesia-based slaglines, it
is not a requirement for dolomite slaglines where only CaO saturation is required. It is
therefore possible to create low-MgO, but CaO-saturated slags, that could have
considerable better desulfurization properties than the dual saturated slags.

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The evaluation of the effect of CaF2 on dual saturated steelmaking slags is difficult since
very limited phase diagrams are available for these complex systems. The few diagrams
that are available will be utilized but in most cases the phase relations will be inferred
from the lower order systems.
Consider the CaO-MgO-SiO2-CaF2 system
The inferred phase relations for this system at 1600C are shown in the next figure.

SiO2 + CaF2
10

90

20

80
S+L

30

70

40

60
50

50
60
Ca2SiO4

Mg2SiO4
40

5% CaF2
8% CaF2

70
Ca3SiO5

30

12% CaF2

80

20

90

CaO

10

10

20

30

40

50

60

70

80

90

MgO

Figure 12. The system CaO-MgO-SiO2-CaF2 at 1600C


This diagram shows the following important features:
1. An increase in CaO solubility as the CaF2 content of the slag increases
2. A decrease in CaO solubility on the CaO-saturation curve as the MgO content of the
slag increases towards dual saturation.
3. An increase in MgO solubility at dual saturation as the CaF2 content of the slag
increases.
One of the most important features of this diagram is the increase in MgO solubility (at
dual saturation) as the CaF2 content of the slag increases. This has significant
implications for magnesia-based slaglines. If fluorspar-containing slags are in contact
with magnesia refractories, then significant refractory wear can occur if the slag is not

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MgO or CaO saturated. If the slag is CaO-saturated but MgO-unsaturated (creamy


consistency), then the extent of refractory wear could be minimized even though the slag
is not fully chemically compatible with the refractories. However, if the slag is also CaO
unsaturated (very liquid or watery in consistency) then severe refractory wear can
occur in just one heat. The above is true for any slag, CaF2-containing or not, but the
presence of CaF2 accelerates the wear because of its depression of the solidus
temperature of the slag, which causes deeper penetration into the refractory matrix.
Consider the CaO-MgO-Al2O3-CaF2 system
It was shown earlier in the CaO-Al2O3-CaF2 system that the addition of CaF2 did not
increase the solubility of CaO. Similar phase relations are observed in the CaO-MgOAl2O3-CaF2 system, which is shown in the next figure.

Figure 13. Phase diagram of the CaO-MgO-CaO-CaF2 system at 10% Al2O3


The compositions of the slags at dual saturation in the systems CaO-MgO-Al2O3 and
CaO-MgO-Al2O3-CaF2 are shown in the next table. The addition of CaF2 to the CaOMgO-Al2O3 system results in only a small increase in the solubility of CaO but a very
large increase in the solubility of MgO in the slag. This diagram and table once again
demonstrate the vulnerability of magnesia-based slagline refractories to CaF2-containing
slags. The use of CaF2 in high-Al2O3 slags therefore should be avoided if possible. The
benefits of using CaF2 as a cheap fluxing precursor might be offset by the potential of
increased refractory wear.

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Table 12. Slag compositions at dual saturation in the systems


CaO-MgO-Al2O3 and CaO-MgO-Al2O3-SiO2 at 1600C.

% CaO
% MgO
% Al2O3
% CaF2

CaO-MgO-Al2O3
system
53
10
37

CaO-MgO-Al2O3-CaF2
system
56
22
10
12

The extent of MgO-dissolution and refractory wear can be minimized if CaO-saturation is


maintained at all times, but if the slag is both CaO and MgO unsaturated (very watery)
then extensive refractory wear could occur.
Summary and Conclusions
The use of fluorspar in steelmaking is a controversial issue. A number of studies have
shown that there are considerable environmental concerns regarding the use of fluorspar,
and many plants has opted not to use fluorspar for this very reason. While fluorspar has
been banned as a deliberate additive to the slags in these plants, the presence of fluorspar
in mold fluxes has not been eliminated.
This paper is not an attempt to justify the use of fluorspar in steelmaking but is rather
geared to provide a better understanding on the behavior of CaF2 for the steel plants that
still use this component.
Fluorspar can be very effective to increase the solubility of CaO in silicate slags but is not
very effective to increase CaO solubility in aluminate slags. The method of fluorspar
addition could have a big impact on the effectiveness of fluorspar to bring lime into
solution and the amounts required to do so. Fluorspar should never be added in its pure
form to a slag but rather in combination with lime and silica. Lime, silica, and CaF2
mixtures are much more effective to go into solution than lime and CaF2 mixtures.
The addition of fluorspar to silicate and aluminate slags results in an increase in the
solubility of MgO in the slag. This increase in MgO solubility could lead to significant
refractory wear if additional MgO is not added to the slag or if CaO-saturation is not
maintained at all times. Most steelmaking refining slags are not MgO-saturated, because
only lime is typically available as an additive. Furthermore, the very high levels of MgO
required for saturation might be undesirable from a steel quality perspective. High MgO
slags in contact with steel with low oxygen content could result in Mg pickup in the steel
and lead to spinel inclusion formation in the steel. Based on the discussion above, it is
clear that dolomite refractories might be more compatible in contact with fluorspar
containing slags than magnesia-based refractories. The simple reason is that lime
saturation (a dolomite refractory requirement) is much easier to achieve in practical
steelmaking than MgO, or dual saturation.

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