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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 composition of the slags is demonstrated. of steel in the basic electric furnace are of a very complex composition and constitution. These slags are only partly derived from the fusion of the nonmetallic materials present in the scrap; they derive far more from the lime and silica added in order to enable the formation of a slag with opportune physicochemical characteristics. The metal-slag-gas processes that take place during steel making have been amply studied with thermodynamic methods. ~-3 These present us with indications for choosing the most favorable range of slag composition for the fulfilment of metallurgical requirements. However, the thermodynamic approach always refers to conditions of equilibrium, and gives no indication about the course of the processes in different situations, as occurs very often in industrial practice. With regard to this a deeper knowledge of the constitution of the slags is necessary, so as to be able to correlate it with their physicochemical properties and with their behavior. As it is somewhat difficult to examine directly the slags in the molten state, generally this type of study is performed on solid samples obtained via quenching from the molten state. Examinations of mineralogical type upon such samples have produced evidence that the slags can be made up of an ensamble of heterogeneous phases. 4,5 In order to describe the reactivity and behavior of these slags, one has had to resort to semiempirical parameters such as the "basicity", the "base-excess ''6,7 and the "free oxygen mole n u m b e r " of the ionic theory, s From the technological point of view, perhaps the most interesting characteristic of the slags is their oxidizing power expressed by the "activity of the F e O " ; the influence of the composition on such a parameter is represented in well known ternary diagrams where the slag is described as belonging to the simplified system (CaO-MgO)-(SiO2 + 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
THE slags formed during the manufacture
varied, the structural situation can change notably and hence the behavior of the iron ions can change remarkably. In order to clarify this problem the following aspects remain to be looked at more closely: a) the type of iron ion effectively present and the influence of the composition and of the degree of oxidation on the Fe2+/Fe 3+ ratio; b) the structural situation of the different iron ions: whether associated with " a c i d " components (silica) and with what coordination, or with " b a s i c " components (lime, magnesium oxide, and so forth). For this type of investigation to be carried out on samples obtained by quenching, we applied MOssbauer Effect Spectroscopy (MES) which is able to supply detailed information directly, without any manipulation of the samples, about the surroundings of the iron atoms. This technique has already been applied to similar problems, although concerning less complex materials, such as the study of the distribution of ferrous and ferric ions in tetrahedral and octahedral sites in the structure of vitreous and crystalline silicates and phosphates 1~ and in the structures of the various types of iron oxides. ~4 EXPERIMENTAL PROCEDURES Slag samples were taken during the various phases and particularly during the blowing of the oxygen of heats of carbon steels in a 40 ton electric furnace. These samples were then cooled rapidly by pouring them onto a water-cooled steel plate. The spectra of powders ground in a mortar were obtained at room temperature in transmission geometry using a conventional spectrometer with constant acceleration, coupled to a muitichannel analyser operating in time mode. The analysis of the spectra was performed with a best fit computer program based on the least-square method. 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 the start of blowing, samples number 2 are intermediate and samples number 3 were taken at the end of blowing. Naturally, given the modest amount of
VOLUME 12B, JUNE 1981--403
E. RAMOUS, Professor, G. PRINCIPI, M. MAGRINI, and A. TIZIANI, Associate Professors, are with lstituto di Chimica Industriale, Universit~t di Padova, Padova, Italy. Manuscript submitted July 18, 1980. METALLURGICAL TRANSACTIONS B
ISSN 0360-2141 / 81/0611-0403500.75/0 9 1981 AMERICAN SOCIETY FOR METALS AND THE METALLURGICAL SOCIETY OF AIME
03 1.82 .06 1. As can be noted from the tabulated values.7 12.16 .30 1.5 11.80 .Table Slag At A2 A3 Bl B2 B3 CI C3 DI D3 EI E3 F3 I.32 1.0~ 'C) ? oOe ~ q SiO 2 29 21 18 28 26.30 .30 .0 18.26 -..16 .5 5.03 1.06 1.0 14.0 16.64 .3 20.17 .85 oo o 1 f.5 43 81 94 75 81 80 50 61 QS/2 1.5 8 10 -10 9 4 26 24 IS 1.0 10.05 1.05 .03 . 4 0 4 .33 .5 12. Figures 1 and 2 show some typical spectra of slags examined and in Table II are reported the MOssbauer parameters corresponding to the best fit for all the samples.06 1. IS and QS in mm/s.79 . of components. and the quadrupole splitting (QS) which is nonzero for certain electronic configurations and also when the iron atoms sit at a site of noncubic symmetry.28 Isomer shifts are referred to ct-Fe centroid. ( M M / S ) Fig. for the most part one is dealing with compositions that stay within the limits for oxidized slags from the basic electric furnace.08 1.02 1.5 15 9.60 .5 16.0 19. Slag E 1 has a magnetic component (about 13 pct) due to presence of metallic iron.43 ---.00 1.00 1.64 1.14 b 2.87 ~_ 1.18 ! | C3 r_3 2.V O L U M E 12B.70 .00 1. QS/2 .1 12.10 1.l _ _ if--I Fe r~+ A 3 q Fe 3+ I I I -- i -2 0 2 4 VEL.5 17.32 . DISCUSSION Interpretation of the Spectra Most of the spectra have the appearance of an unresolved doublet.60 Area pct 44 70 71 61 46.86 .5 12..86 (.78 .16 F 2.30 --.0 13. these samples cannot be considered as representative of the typical composition of the entire slag.30 1. The T a b l e II. Slag 1S A~ A2 A3 B~ B2 B3 C~ C3 DI D3 EI E3 F3 .O t--- ~--7 Fe2* Fe 3 + z 2.70 .65 1.06 1.93 1.5 ~| 0 0 o o o .40 .5 25.08 1.22 1.50 . l ..08 1.69 .76 . Chemical Analysis of the Studied Slags Fe203 12.52 Area pct 8 14 17 -7.62 .66 1. o X ~ 7e: o 16 o~ A I :~ I ] Fe 2+ sample taken with respect to the overall quantity of slag in the furnace.00 .50 .13 .88 E 1.99 QS/2 .M O s s b a u e r spectra of slags A.43 Fe 3. J U N E 1981 METALLURGICAL TRANSACTIONS B .95 .25 1.73 . Several slags with compositions that are unusual due to the high silica content are also inserted into the series with the aim of widening the range o f compositions considered.55 -.70 . with the appearance of unresolved doublets..54 . M6ssbauer Parameters of the Studied Fe 2 -slhcate Slags.38 .58 . but the profile analysis with the best fit computer program leads to consider a variety 1.65 .88 .0 10.32 1.o g ~ ~176 A 1.27 1.71 1.12 ~.40 .5 14. ~ : o o F'a" o ~ * o r .63 .01 1.72 Fe2+-oxide Area pct 48 16 12 39 46 49 9 6 15 10 3 24 15 IS .24 1. Each of them is characterized by its MOssbauer parameters: the isomer shift (IS) which is proportional to the electron density at the nucleus and for example differs from ferrous and ferric states.8 CaO + MgO 37 40 48 40 47 46 58 44 51 60 49 56 54 MnO 8 9 9 4 5 5 6 11 5 9 4 8 7 1. We intend to examine possible heterogeneity of slags inside the furnace in a subsequent work.
55 m m / s inclusive. as was foreseeable.S i O : " F e O " with saturation in lime and or calcium silicates) In such conditions there cannot be a direct correlation between the concentraVOLUME 12B. 3) a doublet with an IS very similar to the previous value and higher QS. however. On the other hand. 1~ The second component is also attributable to Fe E+ as regards the value of the IS. that its relative area is the greatest for all spectra. However. the former with a weak magnetic component ' due to the presence of metallic iron. As a first approximation the percentage contributions can be considered proportional to the concentration of the various forms of iron ions present in the slags (approximation for thin absorbers). in addition. between 2.5 mm/s inclusive. The first component is more difficult to interpret. and the QS value greater than of normal "wustite".76 m m / s inclusive. which were incidentally surprisingly good. For these and other reasons. and the 9 . ( M M / S ) Fig. than as qualitative representations of the interaction tendencies of the various chemical species present in the slags. is not necessarly an equilibrium situation. 2--M6ssbauer spectra of slags E. the " w u s t i t e " .35 I o o o Z 0 o 1. an analogous correlation between the F e : fractions present as mixed oxide and the basic components of the slags (CaO. CaO + MgO. What is not clearly identifiable. The last component can be easily attributed. is the lattice situation of this ion which also differs widely in the various samples. From the diagram in Fig.37 Oo~ o o o o ~ I . for this type of slag the presence has been verified of a phase of "mixed oxides" indicated as RO 4 and made up of solid solutions (FeO-MnOMgO-CaO). whether for the value of the IS or for that of the QS to the Fe E+ in the "silicate glass" phase. given that in our case the iron ion lies in a more asymmetric METALLURGICAL TRANSACTIONS B . best interpretation is obtained imposing as model three components: 1) a singlet or a doublet with small QS and with an IS between 0. corresponding to that of the Fe 2+. 3 one can in fact note that the percentage of F e : present as silicate (pct FeO from analysis x pct Fe 2+ . 2) a doublet with a higher IS.silicate from MES) correlates very well to the silica content in the slags. By attributing the second component to the "mixed oxide" phase one can justify both the value of the IS.39 1. The IS values.45 (D o o o o e o IO 3 .15 and 0. We may observe from Table [I that this is the component with the less spread MOssbauer parameters and.38 1.0 to 1. 4 0 CO I-- o ~ o o ~ o o E 1 o ~ 3.0 mm/s. the QS value is far less than those indicated for the same ion in vitreous phases. On the contrary.1 and 1. as is normally the case. given that splitting varies from 0. only the two high Fe 3+ samples deviated from the overall behavior. for the quantitative data of the MES spectra and the composition of the slags are of significance less on the quantitative side. about 1 m m / s and with QS between 1.0 and 2. it seems to us that the correlations obtained. The values for both the parameters draw close to those attributed to Fe 2+ in an octahedral site in glasses (SiO2-CaO-Na20). One can only state that even in our samples the overall content of " i r o n oxides" is higher in slags at the end of blowing. Correlations Between MES Data and Composition The computer analysis of the MES spectra also supplies an estimation of the contributions given to the spectrum by the various components (see Table II). However. the extent of this influence is not quantifiable in our sample-taking conditions. CaO + MgO + MnO) was not verified. Examining the correlations between these quantities and the comparison of the slags it is necessary to bear in mind that: i) our samples were taken during steelmaking from an industrial furnace. naturally. + latter with an high Fe 3 content. It is possible to justify both results by taking into consideration the fact that practically all the samples examined stay within the zone of the ternary system C a O . JUNE 1981--405 o ~ o o c o o o~ E 3 ~ 0o ~ o ~176 ~o I I'l I Fe2 + I I Fe 3+ I I I I -2 0 2 4 VEL. This indicates that the iron atoms principally belong to the "mixed oxides" phase. too low for the Fe 2+ iron. hence they describe the constitution of the slag existing at that moment and in that particular situation that. In most of the samples the contribution of this component to the spectrum is lower than 10 pct.3. give indication that we are dealing undoubtedly with the Fe 3+ iron. ii) the "degree of oxidation" of the bath and of the slag itself certainly influence the constitution of the slags.] I Fe2 + Fe 3 + o o site in the lattice because of the insertion of other cations. however. the QS is significantly higher with respect to the typical values reported for the simple iron oxide.
S u m m a r i z i n g representation of the Fe 2 distribution between " m i x e d oxides" and "silicate" phases 9 The effect of lime saturation is evident. 9 3--Behavior . into which enters the remaining Fe 2+. 4 we can see that the Fe z+/Fe~Z~ ratio increases with the increase of the basicity ratio B r (CaO/SiO2 by weight). 4 0 6 . The lime and the other basic oxides are divided between the "silicate phase" and the "mixed oxides" phase. it can be seen that in the basic slags the ferrous ion is principally present as a "mixed oxide" as already observed. 6. Fe 2+-slhcate tion of the basic species and the amount of Fe z+. 9 as is shown in Fig. 2) 10 < wt pct SiO2< 20. I 30 9 1 Fig. in Fig. In other words: all the silica present goes to form a "silicate phase" that incorporates a part of Fe 2+. 3) wt pct SiO 2 < 10. On the other hand.2+ % Fesl I 6 5 4 0 9 3 2 _ 1 - I 0 10 I 20 I 30 ~o SI 0 2 Fig. 4 . 3 < B.B e h a v i o r of the Fe2+-oxide/Fe2+-silicate ratio as function of the basicity of the slags: O slags with Fe 3+ > 20 pct. 3) and that in high C a 9 slags an increase in silica rises the FeO activity. The FeE+/Fe~T ratio can also be well correlated to the " F e O activity" obtained from Elliot's diagram. 9 slags with Fe 3 < 20 pct. it is very easy to comprehend that the quantity of Fe z+ related to the silica is proportional to its concentration. As confirmation of the preceeding considerations. J U N E 1981 METALLURGICAL TRANSACTIONS B .. The decreasing behavior can be justified considering that the Fe2~Tpct increases with silica content (see Fig. where the Fe 2§ is prevalently present as "mixed oxide". of p+ercent as function of silica content in the slags: O slags with Fe 3 > 20 pct. It stands out that the Fe2+ pct values for each range of Br are practically independent from the silica content: this means that in our basic slags the C a 9 content. which is greater the higher the silica concentration is. 9 slags with Fe 3+ < 20 pct. . Moreover. It is also possible to give evidence of the influence the slag composition has upon the division of the Fe z+ ion between the "mixed oxides" and the "silicate phase". 5 .1+2 %1/' 3~ 128 _-- 9 9 9 15 : ~ 41 0 I o 9 9 . which gives as the abscissas the silica percentages and as ordinates those of the FeE+. High basicity slags. is the parameter of major influence on the apportion of ferrous ion between the "mixed oxides" and the "silicate phase". 5. Naturally these good correlations between composition of the slags and MES data are an indirect confira~ 2" Feox 20 0[ 16 Feox 2* % Br%3+4 Fesii~ 1--3% Br. which dissolves less Fe 2§ than in the preceding case. one is dealing with slags saturated with a molten calcium silicate..~0 2 + . < 4: the Fe 2§ of the oxide does not seem to relate to the silica content. where the Fe 2§ ion apportions itself between silicate and "mixed oxide". The whole series of results obtained can be summarized and described graphically as in Fig. probably saturated in lime. Here one is dealing with B r of between 1 and 2 inclusive.7.V O L U M E 12B. and only with very low basicity ratios Br (less than 2) does the Fe 2§ ion apportion itself into roughly equal parts between the "oxide phase" and the "silicate phase". 2 I 4 ] 6 J Ca 9 8 so~ [ 0 10 20 % . close or over the saturation. Slags with an intermediate basicity ratio.. Fig. The Fe2o+/Fe2~ ratio can be also correlated with the " silica concentration and clearly diminishes as the silica increases. All the samples can be subdivided into three groups that correspond to three typical situations: 1) wt pct SiO 2 > 25..
Kunugi: J. A. OberhOser: Arkiv.Y. pp. Ward: A n Introduction to the Physical Chemistry o f Iron and Steelmaking. L. H. 3. Inst. and M. 13. 1976. 5 -- ACKNOWLEDGMENTS The authors are indebted to Acciaierie Aveg. 12. and P. J. Lupis and P. N. Alghisi for the care in taking the examined samples. 1956.. pp. R. 2. 2) the Fe 2§ ion distributes itself between a "mixed oxides" phase and a "silicate" phase. J. London-N. 101-05. Y. pp. vol. 134. CONCLUSIONS The application of MES to the study of slags of basic electric furnace has made it possible to establish that: REFERENCES 1. Levy. AIME.3 aFeo Fig. JUNE 1981--407 . Longman. Ron: J.15 Feo x Fes i I 10 2+- 2+ 1) in such slags the iron is present as Fe 2+ with modest amounts of Fe3+. J. chapt. N. Grant. 862. I t . P. Lander. D. Bishop. Bell: Physical Chemistry o f Iron and Steel Manufacture. Yoshimura.. Elliot: Trans. In order to clarify this aspect and in particular the interaction of the ferric ion with the other components of the slag. 8. J. 485. When more drastic conditions of oxidation are reached during the blowing which leads to the formation of considerable quantities of ferric ion. p. 4. 17. A. Met. N. 1946. 1968. Phys. F. vol. pp. 571-76.. Grant and J. and N. 10. 5. von Ende. vol. 14. Res. 1965. Inst. 1967. C. von G. J. Nakagawa.. London. 1976. 1962. 1979. B. AIME. vol. 94-103. C. . 206. Richardson: Physical Chemistry o f Melts in Metallurgy. vol. 17. vol. K. 39. vol.2 mation of the correctness of our interpretation of the MOssbauer spectra. Hillman. Jpn. Hirao. Appl. 1974. 40. Am. This leads one to believe that the correlations described above refer to oxidation conditions of the slags which strongly favor the formation of the ferrous ion. H. Shechter. Tsunawaki. Chem. Ceram. P. 11. Bardenheuer. 3) it is also possible to determine the quantities of the species of iron and to correlate them to the various parameters of the slag composition. G0rI: Stahl Eisen. 13. Academic Press. G. METALLURGICAL TRANSACTIONS B VOLUME 12B. F. T. Tomandl. Arnold Publ. 1950. 62. 167. Soc. + .. Wakabayashi: Trans. + . chapt. Glasses. and J. and H. vol. vol. Weld. N. 6. Ber. p. 109-10. 203.. 37. F. H. pp. the situation of the iron ions in the slag changes appreciably. vol. pp. Matsushita: J. 293-98. G. AIME. 1966. and M. it would be necessary to examine a greater number of slags of a high Fe 3§ content. 1. p. lwamoto. Soga. TrOmel und E. H. Flinn: Phys. 6--Behavior of Fe 2 -Oxlde/Fe2 -sdlcate ratio as function of "FeO activity".. and in particular to Ing. 1955. 1035-51. Italy. These occur however very infrequently in the practical conditions of steelmaking to which our samples refer. Vicenza. H. pp. 3043-47. Bodsworth and H. G. 7 and 8. vol.. J. 5. 1963. Frischat. G. H. 12. Oel: Glastech. 5. H. Chipman: Trans. N. 9. Finally it may be noted that in all the diagrams previously considered the two slags in which the MES measurements verified a high ferric ion content departed from the general behavior. R. Chipman: Trans. p. 7. 14.1 . chapts. vol.
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