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Some aspects for clean steel production

A K lahiri Former Professor IISc, Bangalore, ak_lahiri@yahoo.com Abstract : Often large number of small Al2O3 inclusions are formed in the tundish. As such these are not detrimental to steel but they clog the nozzle resulting asymmetric flow in mold and mold flux entrapment. Proper tundish slag along with electromagnetic break can help to overcome this problem. Introduction Steel with desired low value of impurities like Phosphorus, Sulfur, total oxygen, Nitrogen, Hydrogen and in some grade even carbon is known as clean steel. Among these impurities the behavior of oxygen is different in two ways. After Ladle refining, the other impurities remain almost unchanged but oxygen may increase due to absorption from air or pick up from refractory and slag. Secondly other impurities remain in solution but a significant part of oxygen is present as oxide inclusion so oxygen content is always specified as total oxygen. Since significant part of oxygen is present as inclusion, liquid steel is not homogeneous with respect to oxygen. For number grades both total oxygen and inclusion size should be within a limit. For sheets in tin plate, total oxygen <20ppm and inclusion size <20m, for steel cord used in tires total oxygen <15 and inclusion size <10m, and for ball bearing steel total oxygen <10ppm and inclusion size <15m. So technology of clean steel making is primarily inclusion control. Tundish Since tundish has a pivotal role in the production of clean steel, over the years, large number studies have been made on various aspects of tundish metallurgy. This led to improvement of tundish design with incorporation of flow modifiers like weir, dam, baffles, and turbulence inhibitor or turbo-stop which improved the quality of steel in terms of number of large inclusions present in the final product. However some inherent problem remains.

Oxygen Pick up from air During liquid steel pouring of from ladle to tundish, the shroud prevents exposure of metal stream to atmosphere in the steady state operation. But during initial filling up or during ladle change over, metal is exposed to ambient air. This leads to pick up of oxygen and nitrogen from atmosphere. Fig. 1 shows the change in oxygen level as observed by Solhed1. When pouring starts, there is significant oxygen pick up by metal, which leads to overall increase in oxygen level in tundish. At the outlet oxygen decreases
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200
150

150 100
125

50 0 0 4 8 12

I n le t M id d le O u tle t

100 O (ppm) 75 50 25

0 0 20 40 T im e (m in ) 60 80 100

Figure 1: Variation of total oxygen content at the inlet, middle and outlet with time. Ladle was changed at 40th and 83rd minute. monotonically from ~50ppm at the start to ~15ppm at the time of ladle change over. Again immediately after ladle change over, it increases to a high value and then monotonically decreases. This trend is present for second change over as well confirming significant oxygen pick up from ambient air. This leads to more inclusion in first slab and immediately after ladle change over. It sometimes leads to cluster of iron oxide, Fig2.

Fig.2 Cluster of Iron oxide in the first slab Tundish covering slag Figure 3 schematically shows that covering slag in contact with steel is liquid but that in contact with atmosphere is solid. The liquid slag prevents oxygen transfer from air and readily absorbs oxide inclusion. So the ideal tundish slag should cover steel surface with a liquid slag from the beginning

Fig.3 Schematic diagram of tundish covering slag in a tundish so that it prevents oxygen diffusion from atmosphere and can absorb the inclusion. But in reality this is rarely the case. If liquid slag is formed by the end of first ladle tapping, it is considered as a good covering slag since sometimes it is formed only during tapping of third or fourth ladle. Besides slag should have high dissolution rate and solubility for the inclusions and should not react with the dissolved elements present in steel. Because of these requirements recently Hollappa et al2 used thermodynamic modeling along with laboratory experiment to develop chemistry of active tundish slag. Although the technique is useful to design the chemistry of ideal tundish covering slag but its usage may be limited due to two reasons: firstly it has to be cost effective and secondly number of factors including particle

size distribution of the powder controls the liquid slag formation. So it will require practical modification. Both acidic as well as basic fluxes are used as covering slag. Kijac et al 3 showed that basic slag is more effective than silico aluminate type slag in removing Al2O3 inclusions but even basic slag eventually gets saturated with Al2O3 . Slag metal interaction Slag and metal form two separate layers but slag metal interface may not be smooth and a mixed domain may exist close to interface because of highly turbulent flow due to Kelvin-Helmholtz interfacial instability. The stability condition for the present system is given by 4,5.
(U m U s ) 2 < 2

m s

m s g ( m s ) m s

(1)

where Um, Us and m, s are respectively velocity, density of metal and slag, g is the acceleration due to gravity, m-s is the interfacial tension between metal and slag. m = m/(m+s) and s = s/(m+s) are relative density of metal and slag respectively. Assuming, m-s = 1.5N/m m =7500 kg/m3 and s = 2500kg/m3, the stability criteria becomes (Um Us)< 0.64 m/s (2)

At the slag metal interface, the velocity is higher than this, so disturbances can grow to form waves and lead to emulsification or mixed zone formation. Fig.4 shows the result reported by Solhed1. It shows a mixed zone as a dark

Macroscopic slag removed Steel

Mixing zone

Fig.4 Mixing Zone. The dark portion in the middle is mixing zone1

region above the metal phase. The thickness of mixing zone is about 100m close to inlet but in other areas, the size is smaller. The thickness of mixed zone in Fig.4 is about 30. Mixed zone is layered with Al2O3 inclusions in the upper part. Most of the inclusions present here are less than 10m. Similar observation was reported by Solhed6 earlier. Fig.5 shows the interface. It shows that in microscopic scale the interface is not flat and

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Figure 5 slag metal interface1

inclusions are present at the interface. Small globular slag lumps and inclusions could be seen close to interface. Fig.6 shows that these inclusions are CaO, Al2O3 and CaO.Al2O3. The presence of CaO.Al2O3 inclusions suggest that at the interface Al2O3 reacts with CaO present in slag to form these inclusions. Small Al2O3 inclusions might have formed by the reaction of aluminum with FeO in slag or dissolved oxygen. Since the sizes of globular slag lumps are very small, and no big lump was observed, the origin of these lumps could be interfacial instability or due to the impact of high energy small eddies present in the metal. Solhed et al7 showed by mathematical modeling that the recirculation flow at the inlet region can also lead to slag entrapment in metal and metal entrapment in slag. However only small fraction of these can reach the outlet. It is well known that ladle slag infiltrates into the tundish. This leads to increase in CaO even in silico aluminate type tundish covering slag besides

it increases FeO content of tundish slag resulting in formation of Al2O3 inclusions.

Fig.6 Inclusions close to interface. Whitish ones are Al2O3 and black ones are CaO and partly whitish and partly blackish ones are CaO.Al2O31. Table 2 shows inclusion count of samples from ladle furnace and two locations of tundish. The increase of small size inclusion <10m in the tundish is apparent. Obviously they formed in the tundish. The analysis of these inclusions shows they are mostly either Al2O3 or CaO or Al2O3.CaO. It further indicates that some smaller inclusion can become bigger in tundish by coagulation and get removed in the tundish itself. Table 11 Inclusion count in Ladle furnace and tundish Location Ladle Furnace Tundish Left Tundish Mid <10m/mm 172.7 544.3 1046.9
2

Inclusion 10-50m/mm2 5.6 2.2 4.9

Size >50m/mm2 0 0.07 0.07

Refractory metal interaction Refractory is another source of oxygen pick up. MgO based refractories used in tundish contain olivine which is a solid solution of fayalite (Fe2SiO4) and forsterite (Mg2SiO4). These can react with de-oxidized steel according to following reactions: Fe2SiO4 = 2Fe + 2O + SiO2 Mg2SiO4 + SiO2 = 2(MgSiO3) 2Al + 3O = Al2O3 MgO + Al2O3 = MgAl2O4 Pack et al8 studied used tundish refractory by electron probe micro analysis, TEM and back scattered electron images. They found olivine where its faylite component is reduced, Fig.7 Besides they observed Mg2SiO3 and MgAl2O4 and concluded that all the above mentioned reactions take place in the tundish.

Fig.7 TEM of olivine in contact with liquid steel containing 0.04%Al8 Mould Although under ideal operating condition, inclusions particularly Al2O3 should get removed in the mould but in reality sometimes a significant amount of exogenous inclusion gets trapped into metal. Fluid flow characteristic in the mould has a major role in it.

Absorption of inclusion Mold flux picks up about 4% Al2O3. Part of it is de-oxidation product and part of it is formed by the reaction: 1.5 SiO2 (flux) + [Al] = Al2O3 + 1.5 [Si] However in case of special steel which contains high Al, pick up of Al2O3 is much higher and thereby the resulting flux will have different property compared to original flux. SEN clogging It is well established that Al2O3 inclusions deposit on inner wall of nozzle and clog it. Fig.8 shows original as well as clogged nozzle as reported by Rodl et al9. It shows that inclusions deposit primarily at the discharge end of the nozzle and blocks the port partly.

Fig 8 Nozzle clogging9 Fig 9 shows that discharge from the port of clogged nozzle and flow in the mold is highly asymmetric and complex. Asymmetry is very significant

Fig 9 Computed result of clogged nozzle9 on the top surface where a region on one side has a high velocity. Longs 10 model showed that only inclusions below 15m can deposit on the nozzle. Al2O3 inclusions deposited on SEN sometimes get dislodged and gets entrapped in metal as large inclusion. Figure 10 shows one such case. It is interesting to note that inclusions in the cluster are <10 m which supports

Fig.10 SEM of a defective region. Clusters of small Al2O3 inclusions1.

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Longs result. This along with the observation of Rodl9 that number of inclusions, not total inclusions, play a major role in clogging suggest that Al2O3 formed in tundish due to oxygen influx has a major role in clogging. Flux entrapment Fig. 11 shows schematically shows top surface of mold. The wave shown on the top is not a standing wave but it oscillates. Because of the shear force

Fig 11 Schematic diagram of flux metal interface in the mould at the slag metal interface liquid flux can get entrained either because of wave instability or vortex formation as shown in Fig 12(a) and (b) respectively. These happen only at high metal velocity at the meniscus.

(a) (b) 11 Fig 12 Flux entrainment by sharing and vortex formation Possibility of slag entrapment by these mechanism becomes less for high viscosity of mold slag. Besides the above two mechanisms of slag entrainment, solid flux gets entrained in the metal if amplitude of wave is more than the liquid slag layer

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thickness. In this case part of meniscus metal becomes bald as shown in Fig 13(a) thereby when solid flux is added there, it directly gets entrained in metal, Fig 13(b)12. This can be avoided by maintaining proper thickness of liquid flux layer.

(a)

(b)

Fig 13 Flux entrainment due to balding of meniscus (a) balding (b) Flux entrainment It has been pointed out earlier that nozzle clogging leads to asymmetric flow and can lead to significant disturbances in meniscus. This could lead to flux entrapment. Sometimes it is found that even at the apparently steady casting condition strand quality is below par. This could be attributed to asymmetric flow through the ports due to nozzle clogging. Flux can get entrapped in metal due to Kelvin Helmoltz instability although there is no direct evidence for it. Discussion Improved tundish design helped in reducing large inclusion from the steel. But due to various mechanisms of oxygen input in the tundish, a large number of fine Al2O3 inclusions <10m are generated there. A significant part of these deposit in the lower part of SEN and make fluid discharge from the ports asymmetric. This asymmetric flow has a major role in mold flux entrapment and reducing the cleanliness of steel. Some of the inclusions deposited in the SEN come out as a cluster and form big inclusion in steel. Prevention of oxygen input into the tundish and making sure that tundish slag absorbs significant amount of Al2O3 inclusion will reduce fine inclusions. Both these require an early liquid slag formation in the tundish

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with high Al2O3 absobing capacity. Basic slag satisfy these requirements but more research is needed to see that slag formation is early enough. Ca treatment is widely used to prevent the nozzle clogging. But investigation of Rodl9 showed that some CaO form CaO.2Al2O3 which has melting point of 1705C and these inclusions deposit on SEN. The deposition of inclusion on SEN makes the fluid flow in the meniscus complex and leads to high meniscus velocity which may lead to flux entrainment. Only reduction of velocity at the meniscus can prevent flux entrainment. So electro-magnetic break and SEN design to give swirling flow are the available options. A simpler option of course is the increase of port diameter but there is practical limitation to this. Conclusion Suitable tundish flux development which will lead to early liquid slag formation in tundish along with high Al2O3 absorption capacity will go long way in producing cleaner steel. References 1. Henrik Solhed, Pranesh Dayal, A.K.Lahiri : Int Conf on Continuous Casting Past, Present & Future, Jamshedpur, 24- 25th October 2005 2. L. Hollappa et al : Steel Res Int. published on line on 18th Feb.2013 3. J. Kijac et al : Metalurgija vol 43 2004 p 59 4. S. Chandrasekhar: Hydrodynamics and Hydromagnetic stability, Dover Pub. N.Y.,1961 p485 5. Y.Chung and A.W.Cramb: Metall Mater. Trans. Vol.31B (2000) p957 6. H.Solhed, L. Jonsson and P.Jonsson : Metall Mater. Trans. Vol.33B 2002 p17 7. H.Solhed, L. Jonsson and P.Jonsson : Steel Res. Int. 2008 vol 79 p 348 8. A. Pack, S.Hoernes and Th Walther: Proc. 6th Int. congress on Applied Mineralogy, Gottingen, Germany, 17-19 July 2000 p518 9. S. Rodl et al : New strategies for clogging prevention for improved productivity of Steel, EU report 2012 10. M. Long et al ISIJ Int. 2010 vol 50 p712 11. D Gupta and AK Lahiri: Ironmaking- Steelmaking 1996, vol 23 p361 12. D Gupta and AK Lahiri:Metall Trans.B, 1996 vol 27B p 695