Professional Documents
Culture Documents
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
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
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.
% 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.
75
Slag (a) in Fig. 2
% CaO in Solution
70
65
60
55
50
10
15
20
25
30
35
40
% SiO2
% 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.
% CaO
% Al2O3
% CaF2
Slag (a)
61
39
Slag (b)
50
30
20
% CaO
% SiO2
% CaF2
% Al2O3
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.
11
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
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 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.
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
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.
Temperature (C)
1600
1500
1400
1353
1300
MgO
20
40
60
80
CaF2
Wt% CaF2
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
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
20
80
S+L
30
70
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
20
10
80
90
MgO
Figure 10. The 1600C isothermal section for the CaO-MgO-SiO2 system
17
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.
18
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
19
20
% CaO
% MgO
% Al2O3
% CaF2
CaO-MgO-Al2O3
system
53
10
37
CaO-MgO-Al2O3-CaF2
system
56
22
10
12
21