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By
Eugene Pretorius
Baker Refractories
Epretorius@bakerref.com
1
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.
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.
2
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:
Table 2. Calculated slag and metal parameters for a CaO-saturated CaO-SiO2 slag
and a pure CaF2 slag at 1600°C.
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.
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.
3
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.
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 following figure shows the phase diagram of the CaO-CaF2 system.
4
This diagram shows a few very important features:
2. An eutectic exists between CaO and CaF2 at 1360°C (°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°(2912°F) 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:
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 1600°C:
Table 4. Amounts of liquid and solid for different CaO-CaF2 mixtures at 1600°C
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?
5
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 1600°C 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 1600°C 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.
6
75
70
% CaO in Solution
65
60
55
50
10 15 20 25 30 35 40
% SiO2
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 1600°C
*The composition of the liquid for mixture 2 only contain about 27% CaO in solution.
7
The combination of CaF2 and SiO2 in the right proportions can create slags in the CaO-
CaF2-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 1600°C.
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 following figure shows the isothermal section of the CaO-Al2O3-CaF2 system at
1600°C.
8
Figure 4. Isothermal section through the CaO-Al2O3-CaF2 system at 1600°C
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 CaO-
Al2O3 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:
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 1600°C.
9
Figure 5. Isothermal section through the CaO-Al2O3-SiO2 system at 1600°C.
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.
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.
10
Table 8. Maximum CaO solubility limits of slags in the CaO-CaF2-SiO2
and CaO-Al2O3-SiO2 systems.
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.
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 high-
Al2O3 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).
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.
11
Table 9. Advantages and disadvantages of different raw material additions
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 high-
Al2O3 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:
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
12
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 Ca-
aluminate and/or carryover slag as fluxing precursors. In the discussion of the CaO-
Al2O3-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.
The solubility of Al2O3 in CaF2 at 1600°C 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”
13
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 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.
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.
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 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 1600°C is about 48 wt%. This is significantly higher
than CaO in the equivalent CaO-CaF2 system (26.6% CaO). The composition of the
14
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.
1600
Temperature (°C) L
1500
1400
1353
1300
MgO 20 40 60 80 CaF2
Wt% CaF2
Figure 7. Redrawn Phase diagram of the MgO-CaF2 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 1600°C 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 1600°C on
the MgO-CaF2 join, and then the 1600°C isotherm can be redrawn as follows:
40%
MgO SiO2
CaF2
MgO 60%
CaF2
Figure 9. Isothermal section at 1600°C 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 1600°C
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.
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.
50 50
M2 S + L
P Mg2SiO4
60 O 40
C2S + L
Ca2SiO4 M+L M2S + L + M
70 C 2S + L + M 30
Ca3SiO5
80 20
Slags compatible with both
90 dolomite and Magnesia-C 10
refractories:
10 MgO
20 3and
0 4CaO-Saturated
0 50 60 70 80 90
CaO MgO
Figure 10. The 1600°C isothermal section for the CaO-MgO-SiO2 system
17
45
1700°C
35
Slag P
30
25
20
Slag O
(Dual Saturated)
15
0.4 0.6 0.8 1.0 1.2 1.4
% 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:
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.
The inferred phase relations for this system at 1600°C are shown in the next figure.
SiO2 + CaF2
10 90
20 80
S+L
30 70
40 60
50 50
Mg2SiO4
60 5% CaF2 40
Ca2SiO4
8% CaF2
70 12% CaF2 30
Ca3SiO5
80 20
90 10
10 20 30 40 50 60 70 80 90
CaO MgO
Figure 12. The system CaO-MgO-SiO2-CaF2 at 1600°C
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
19
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.
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-MgO-
Al2O3-CaF2 system, which is shown in the next figure.
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 CaO-
MgO-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 1600°C.
CaO-MgO-Al2O3 CaO-MgO-Al2O3-CaF2
system system
% CaO 53 56
% MgO 10 22
% Al2O3 37 10
% CaF2 12
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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