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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+
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
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.
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.