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A M ssbauer Study of Electric

Steelmaking Basic Slags


E. RAMOUS, G. P R I N C I P I , M. MAGRINI AND A. T1Z1ANI

M0ssbauer measurements have been made on powder samples of basic slags from a
steelmaking electric furnace. The samples were taken during oxygen blowing. A
prevalence is found of divalent iron in "mixed oxide" form and in the silicate phase. The
ability of M0ssbauer spectroscopy to characterize such heterogeneous materials and to
correlate the distribution of ferrous ions between the oxide and the silicate with the com-
position of the slags is demonstrated.

THE slags formed during the manufacture of steel in varied, the structural situation can change notably and
the basic electric furnace are of a very complex com- hence the behavior of the iron ions can change
position and constitution. These slags are only partly remarkably.
derived from the fusion of the nonmetallic materials In order to clarify this problem the following
present in the scrap; they derive far more from the aspects remain to be looked at more closely:
lime and silica added in order to enable the formation a) the type of iron ion effectively present and the
of a slag with opportune physicochemical characteris- influence of the composition and of the degree of oxi-
tics. dation on the Fe2+/Fe 3+ ratio;
The metal-slag-gas processes that take place during b) the structural situation of the different iron ions:
steel making have been amply studied with thermo- whether associated with " a c i d " components (silica)
dynamic methods. ~-3 These present us with indications and with what coordination, or with " b a s i c " com-
for choosing the most favorable range of slag com- ponents (lime, magnesium oxide, and so forth).
position for the fulfilment of metallurgical re- For this type of investigation to be carried out on
quirements. However, the thermodynamic approach samples obtained by quenching, we applied MOss-
always refers to conditions of equilibrium, and gives bauer Effect Spectroscopy (MES) which is able to
no indication about the course of the processes in dif- supply detailed information directly, without any
ferent situations, as occurs very often in industrial manipulation of the samples, about the surroundings
practice. of the iron atoms. This technique has already been
With regard to this a deeper knowledge of the con- applied to similar problems, although concerning less
stitution of the slags is necessary, so as to be able to complex materials, such as the study of the distribu-
correlate it with their physicochemical properties and tion of ferrous and ferric ions in tetrahedral and oc-
with their behavior. As it is somewhat difficult to ex- tahedral sites in the structure of vitreous and crystal-
amine directly the slags in the molten state, generally line silicates and phosphates 1~ and in the structures
this type of study is performed on solid samples ob- of the various types of iron oxides. ~4
tained via quenching from the molten state. Examina-
tions of mineralogical type upon such samples have
produced evidence that the slags can be made up of EXPERIMENTAL PROCEDURES
an ensamble of heterogeneous phases. 4,5 Slag samples were taken during the various phases
In order to describe the reactivity and behavior of and particularly during the blowing of the oxygen of
these slags, one has had to resort to semiempirical heats of carbon steels in a 40 ton electric furnace.
parameters such as the "basicity", the These samples were then cooled rapidly by pouring
"base-excess ''6,7 and the "free oxygen mole n u m b e r " them onto a water-cooled steel plate.
of the ionic theory, s From the technological point of The spectra of powders ground in a mortar were
view, perhaps the most interesting characteristic of the obtained at room temperature in transmission geom-
slags is their oxidizing power expressed by the "activity etry using a conventional spectrometer with constant
of the F e O " ; the influence of the composition on acceleration, coupled to a muitichannel analyser
such a parameter is represented in well known ternary operating in time mode. The analysis of the spectra
diagrams where the slag is described as belonging to was performed with a best fit computer program based
the simplified system (CaO-MgO)-(SiO2 + on the least-square method.
AI203)-"FeO". 9 These diagrams bring to light how the
"activity of the F e O " is strongly dependent upon the
composition of the slag, since evidently, if this is RESULTS
In Table I the compositions of the samples examined
are shown. Samples from different heats were marked
with a letter. Samples number 1 refer to slags taken at
E. RAMOUS, Professor, G. PRINCIPI, M. MAGRINI, and A.
TIZIANI, Associate Professors, are with lstituto di Chimica Indus-
the start of blowing, samples number 2 are inter-
triale, Universit~t di Padova, Padova, Italy. mediate and samples number 3 were taken at the end
Manuscript submitted July 18, 1980. of blowing. Naturally, given the modest amount of
ISSN 0360-2141 / 81/0611-0403500.75/0
METALLURGICAL TRANSACTIONS B 9 1981 AMERICAN SOCIETY FOR METALS AND VOLUME 12B, JUNE 1981--403
THE METALLURGICAL SOCIETY OF AIME
Table I. Chemical Analysis of the Studied Slags 1.88 E
CaO + 1.87 ~_
? oOe ~ q
~|
Slag SiO 2 Fe203 MgO MnO 00 o o
o ,,o g
At 29 12.0 37 8 1.86 ~ ~176
A2 21 14.0 40 9 A
A3 18 18.0 48 9 (.0~ 1
Bl 28 10.0 40 4 'C)
1.85
oo
B2 26.5 10.5 47 5 o
B3 25.5 11.0 46 5
CI 12.5 13.3 58 6 f.O ~--7 Fe2*
Fe 3 +
C3 5.5 20.1 44 11 t---
DI 17.5 12.0 51 5 z 2.18
D3 15 16.0 60 9 C3 ! |
EI 9.7 19.5 49 4 r_3
E3 12.5 16.5 56 8 2.16 F o Xo~176e:
F3 12.5 14.8 54 7
2.14 b o~ A
I :~
2.12 ~.
sample taken with respect to the overall quantity of I ] Fe 2+

slag in the furnace, these samples cannot be con- 1.66 ~ F'a"


sidered as representative of the typical composition of
the entire slag. We intend to examine possible hetero- 1.65 , :
geneity of slags inside the furnace in a subsequent o o o
work. 1.64 ~ * A
As can be noted from the tabulated values, for the 3
most part one is dealing with compositions that stay 1.63 o
within the limits for oxidized slags from the basic r - - l _ _ Fe r~+

electric furnace. Several slags with compositions that if--I q Fe 3+

are unusual due to the high silica content are also in-
serted into the series with the aim of widening the
range o f compositions considered. I I I -- i

Figures 1 and 2 show some typical spectra of slags -2 0 2 4


examined and in Table II are reported the MOssbauer VEL. ( M M / S )
parameters corresponding to the best fit for all the Fig. l - - M O s s b a u e r spectra of slags A, with the appearance of
samples. unresolved doublets.

DISCUSSION of components. Each of them is characterized by its


MOssbauer parameters: the isomer shift (IS) which is
proportional to the electron density at the nucleus and
Interpretation of the Spectra
for example differs from ferrous and ferric states, and
Most of the spectra have the appearance of an the quadrupole splitting (QS) which is nonzero for
unresolved doublet, but the profile analysis with the certain electronic configurations and also when the
best fit computer program leads to consider a variety iron atoms sit at a site of noncubic symmetry. The

T a b l e II. M6ssbauer Parameters of the Studied Slags.

Slag Fe 3. Fe 2 -slhcate Fe2+-oxide


1S QS/2 Area pct IS QS/2 Area pct IS QS/2 Area pct
A~ .16 .33 8 1.13 1.24 48 .93 .88 44
A2 .40 .30 14 .95 1.08 16 1.05 .60 70
A3 ,55 .43 17 .71 1.25 12 1.00 .54 71
B~ -- -- -- 1.03 1.02 39 1.06 .62 61
B2 .17 -- 7.5 1.00 1.06 46 1.08 .64 46.5
B3 .16 -- 8 1.00 1.06 49 1.08 .65 43
C~ .26 .30 10 .86 1.27 9 1.03 .70 81
C3 -- -- -- .78 1.32 6 1.00 .70 94
DI .05 -- 10 .79 1.30 15 1.06 .69 75
D3 .32 .40 9 .82 1.30 10 1.01 .73 81
EI .30 .38 4 .80 1.32 3 1.10 .76 80
E3 .58 .50 26 .70 1.22 24 1,03 .50 50
F3 .43 .52 24 .72 1.28 15 .99 .60 61
Isomer shifts are referred to ct-Fe centroid. Slag E 1 has a magnetic component (about 13 pct) due to presence of metallic iron. IS and QS in
mm/s.

4 0 4 - - V O L U M E 12B, J U N E 1981 METALLURGICAL TRANSACTIONS B


site in the lattice because of the insertion of other
cations.
We may observe from Table [I that this is the com-
3.45 o
o
e
ponent with the less spread MOssbauer parameters
o
o o
and, in addition, that its relative area is the greatest
(D o o E for all spectra. This indicates that the iron atoms
IO 3 . 4 0 ~ o ~ 1
principally belong to the "mixed oxides" phase.
o o
~
o The first component is more difficult to interpret.
CO 3.35 o
o
o The IS values, too low for the Fe 2+ iron, give indica-
I-- tion that we are dealing undoubtedly with the Fe 3+
Z iron. What is not clearly identifiable, however, is the
0 I I Fe2 + lattice situation of this ion which also differs widely in
o ~ .] I Fe 3 +
the various samples, given that splitting varies from
0.0 to 1.0 mm/s. In most of the samples the contribu-
1.39 Oo~ tion of this component to the spectrum is lower than
o
o
o 10 pct.
o
o
1.38 o
o E Correlations Between MES Data
~o ~ 3
o
and Composition
1.37 c o o o~
The computer analysis of the MES spectra also sup-
~176
0o
~ ~o plies an estimation of the contributions given to the
o
spectrum by the various components (see Table II).
I'- I +
l I Fe2
As a first approximation the percentage contributions
I I Fe 3+
can be considered proportional to the concentration
of the various forms of iron ions present in the slags
(approximation for thin absorbers).
I I I I Examining the correlations between these quantities
-2 0 2 4 and the comparison of the slags it is necessary to bear
in mind that: i) our samples were taken during steel-
VEL. ( M M / S ) making from an industrial furnace; hence they
Fig. 2--M6ssbauer spectra of slags E, the former with a weak
magnetic9 component due to the presence of metallic iron, and the
describe the constitution of the slag existing at that
. ' +
latter with an high Fe 3 content. moment and in that particular situation that, naturally,
is not necessarly an equilibrium situation; ii) the
"degree of oxidation" of the bath and of the slag
best interpretation is obtained imposing as model itself certainly influence the constitution of the slags;
three components: however, the extent of this influence is not quantifi-
1) a singlet or a doublet with small QS and with an able in our sample-taking conditions. One can only
IS between 0.15 and 0.55 m m / s inclusive; state that even in our samples the overall content of
2) a doublet with a higher IS, about 1 m m / s and " i r o n oxides" is higher in slags at the end of blowing,
with QS between 1.1 and 1.76 m m / s inclusive; as is normally the case.
3) a doublet with an IS very similar to the previous For these and other reasons, it seems to us that the
value and higher QS, between 2.0 and 2.5 mm/s correlations obtained, which were incidentally surpris-
inclusive. ingly good, for the quantitative data of the MES spec-
The last component can be easily attributed, whether tra and the composition of the slags are of signifi-
for the value of the IS or for that of the QS to the cance less on the quantitative side, than as qualitative
Fe E+ in the "silicate glass" phase. The values for both representations of the interaction tendencies of the
the parameters draw close to those attributed to Fe 2+ various chemical species present in the slags.
in an octahedral site in glasses (SiO2-CaO-Na20). 1~ From the diagram in Fig. 3 one can in fact note
The second component is also attributable to Fe E+ that the percentage of F e : present as silicate (pct FeO
as regards the value of the IS. However, the QS value from analysis x pct Fe 2+ - silicate from MES) cor-
is far less than those indicated for the same ion in relates very well to the silica content in the slags; as
vitreous phases. On the other hand, the QS is signifi- was foreseeable, only the two high Fe 3+ samples
cantly higher with respect to the typical values deviated from the overall behavior. On the contrary,
reported for the simple iron oxide, the " w u s t i t e " . an analogous correlation between the F e : fractions
However, for this type of slag the presence has been present as mixed oxide and the basic components of
verified of a phase of "mixed oxides" indicated as the slags (CaO, CaO + MgO, CaO + MgO + MnO)
RO 4 and made up of solid solutions (FeO-MnO- was not verified. It is possible to justify both results
MgO-CaO). By attributing the second component to by taking into consideration the fact that practically
the "mixed oxide" phase one can justify both the all the samples examined stay within the zone of the
value of the IS, corresponding to that of the Fe 2+, and ternary system C a O - S i O : " F e O " with saturation in
the QS value greater than of normal "wustite", given lime and or calcium silicates) In such conditions there
that in our case the iron ion lies in a more asymmetric cannot be a direct correlation between the concentra-

METALLURGICAL TRANSACTIONS B VOLUME 12B, JUNE 1981--405


in the basic slags the ferrous ion is principally present
6
2+ as a "mixed oxide" as already observed, and only
% Fesl I with very low basicity ratios Br (less than 2) does the
5
Fe 2§ ion apportion itself into roughly equal parts be-
tween the "oxide phase" and the "silicate phase".
4
0 9 The Fe2o+/Fe2~" ratio can be also correlated with the
silica concentration and clearly diminishes as the silica
3
increases.
The whole series of results obtained can be sum-
2 _

marized and described graphically as in Fig. 5, which


gives as the abscissas the silica percentages and as or-
1 -

dinates those of the FeE+. All the samples can be sub-


divided into three groups that correspond to three
I I I
0 10 20 30 typical situations:
1) wt pct SiO 2 > 25. Here one is dealing with B r
~o SI 0 2 of between 1 and 2 inclusive, where the Fe 2§ ion ap-
Fig. 9
3--Behaviorof Fe 2+-slhcate
..
p+ercent as function of silica con- portions itself between silicate and "mixed oxide".
tent in the slags: O slags with Fe 3 > 20 pct; 9 slags with Fe 3 < 2) 10 < wt pct SiO2< 20. Slags with an intermediate
20 pct.
basicity ratio, 3 < B, < 4: the Fe 2§ of the oxide does
not seem to relate to the silica content; one is dealing
tion of the basic species and the amount of Fe z+. On with slags saturated with a molten calcium silicate,
the other hand, it is very easy to comprehend that the which dissolves less Fe 2§ than in the preceding case.
quantity of Fe z+ related to the silica is proportional to 3) wt pct SiO 2 < 10. High basicity slags, prob-
its concentration. In other words: all the silica present ably saturated in lime, where the Fe 2§ is prevalently
goes to form a "silicate phase" that incorporates a present as "mixed oxide".
part of Fe 2+, which is greater the higher the silica con- It stands out that the Fe2+ pct values for each range
centration is. The lime and the other basic oxides are of Br are practically independent from the silica con-
divided between the "silicate phase" and the "mixed tent: this means that in our basic slags the C a 9 con-
oxides" phase, into which enters the remaining Fe 2+. tent, close or over the saturation, is the parameter of
It is also possible to give evidence of the influence major influence on the apportion of ferrous ion be-
the slag composition has upon the division of the Fe z+ tween the "mixed oxides" and the "silicate phase".
ion between the "mixed oxides" and the "silicate The FeE+/Fe~T ratio can also be well correlated to
phase". As confirmation of the preceeding considera- the " F e O activity" obtained from Elliot's diagram, 9
tions, in Fig. 4 we can see that the Fe z+/Fe~Z~ ratio as is shown in Fig. 6. The decreasing behavior can be
increases with the increase of the basicity ratio B r justified considering that the Fe2~Tpct increases with
(CaO/SiO2 by weight). Moreover, it can be seen that silica content (see Fig. 3) and that in high C a 9 slags
an increase in silica rises the FeO activity.
Naturally these good correlations between composi-
tion of the slags and MES data are an indirect confir-

16
2*
a~ Br%3+4 Br- 1+2
Feox
% Fesii~ 1--3% %1/' 3~
2"
Feox
20
0[
128 _-- 9 9 9

15

: ~

41
I

o 9 9

.7.
I ] J [ I 1
0 2 4 6 Ca 9 8 0 10 20 30
so~ % ,~0 2
+ . . 9
Fig. 4 - - B e h a v i o r of the Fe2+-oxide/Fe2+-silicate ratio as function of Fig. 5 - - S u m m a r i z i n g representation of the Fe 2 distribution be-
the basicity of the slags: O slags with Fe 3+ > 20 pct; 9 slags with tween " m i x e d oxides" and "silicate" phases 9 The effect of lime
Fe 3+ < 20 pct. saturation is evident.

4 0 6 - - V O L U M E 12B, J U N E 1981 METALLURGICAL TRANSACTIONS B


1) in such slags the iron is present as Fe 2+ with
modest amounts of Fe3+;
15
2) the Fe 2§ ion distributes itself between a "mixed
2+
oxides" phase and a "silicate" phase;
Feo x 3) it is also possible to determine the quantities of
2+-
Fes i I the species of iron and to correlate them to the
various parameters of the slag composition.
10 -

5 --
ACKNOWLEDGMENTS
The authors are indebted to Acciaierie Aveg, Vicenza,
Italy, and in particular to Ing. Alghisi for the care in
taking the examined samples.
I t
.1 .2 .3
aFeo
+ . + ..
Fig. 6--Behavior of Fe 2 -Oxlde/Fe2 -sdlcate ratio as function of
"FeO activity".

REFERENCES
mation of the correctness of our interpretation of the
MOssbauer spectra. 1. C. Bodsworth and H. B. Bell: Physical Chemistry o f Iron
Finally it may be noted that in all the diagrams and Steel Manufacture, chapt. 12, Longman, 1965.
2. R. G. Ward: A n Introduction to the Physical Chemistry o f
previously considered the two slags in which the MES Iron and Steelmaking, chapt. 5, Arnold Publ., London,
measurements verified a high ferric ion content 1962.
departed from the general behavior. This leads one to 3. F. D. Richardson: Physical Chemistry o f Melts in
believe that the correlations described above refer to Metallurgy, vol. 1, chapts. 7 and 8, Academic Press,
London-N.Y., 1974.
oxidation conditions of the slags which strongly favor 4. G. TrOmel und E. G0rI: Stahl Eisen, 1963, vol. 17, pp.
the formation of the ferrous ion. 1035-51.
When more drastic conditions of oxidation are 5. F. Bardenheuer, H. von Ende, and P. G. OberhOser: Arkiv,
reached during the blowing which leads to the forma- 1968, vol. 39, pp. 571-76.
6. N. J. Grant and J. Chipman: Trans. AIME, 1946, vol. 167,
tion of considerable quantities of ferric ion, the situa-
p. 134.
tion of the iron ions in the slag changes appreciably. 7. H. L. Bishop, H. N. Lander, N. J. Grant, and J. Chipman:
In order to clarify this aspect and in particular the in- Trans. AIME, 1956, vol. 206, p. 862.
teraction of the ferric ion with the other components 8. J. Matsushita: J. Jpn. Inst. Met., 1950, vol. 13, p. 14.
of the slag, it would be necessary to examine a greater 9. J. F. Elliot: Trans. AIME, 1955, vol. 203, p. 485.
10. von G. Tomandl, G. H. Frischat, and H. J. Oel: Glastech.
number of slags of a high Fe 3§ content. These occur Ber., 1967, vol. 40, pp. 293-98.
however very infrequently in the practical conditions 11. R. A. Levy, C. H. P. Lupis and P. A. Flinn: Phys. Chem.
of steelmaking to which our samples refer. Glasses, 1976, vol. 17, pp. 94-103.
12. K. Hirao, N. Soga, and M. Kunugi: J. Am. Ceram. Soc.,
1979, vol. 62, pp. 109-10.
CONCLUSIONS 13. N. lwamoto, Y. Tsunawaki, H. Nakagawa, T. Yoshimura,
and N. Wakabayashi: Trans. J. Weld. Res. Inst., 1976, vol.
The application of MES to the study of slags of 5, pp. 101-05.
basic electric furnace has made it possible to establish 14. H. Shechter, P. Hillman, and M. Ron: J. Appl. Phys.,
that: 1966, vol. 37, pp. 3043-47.

METALLURGICAL TRANSACTIONS B VOLUME 12B, JUNE 1981--407