CN100443215C - Protective slag for ultralow carbon steel continuous casting - Google Patents
Protective slag for ultralow carbon steel continuous casting Download PDFInfo
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- CN100443215C CN100443215C CNB2006100950620A CN200610095062A CN100443215C CN 100443215 C CN100443215 C CN 100443215C CN B2006100950620 A CNB2006100950620 A CN B2006100950620A CN 200610095062 A CN200610095062 A CN 200610095062A CN 100443215 C CN100443215 C CN 100443215C
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Abstract
The ultra-low carbon steel protecting slag for continuous casting consists of carbon material 0.5-1.6 wt%, metal smelting speed regulator 2-8 wt%, MgO 2-7 wt%, Na2O 6-12 wt%, F- 2-8 wt%, Al2O3 2-7 wt%, MnO 3-8 wt%, Fe2O3 1-3 wt%, except CaO and SiO2, where the weight ratio CaO/SiO2 is 0.75-1.05. The metal smelting speed regulator is one of Ca-Si alloy, Ca-Ba-Si alloy, Mn-Si alloy and Fe-Mn alloy or any composition of them. The ultra low carbon steel protecting slag is used for continuous casting, and has synergistic metallurgical functions and no carburization of the continuous cast billet.
Description
Technical field
The present invention relates to a kind of covering slag that continuous cast crystallizer uses of making steel, relate in particular to the covering slag that its carbon content of continuous casting is less than or equal to the ultra-low-carbon steel of 50ppm.
Background technology
Regulate material by base-material, flux and burn-off rate, through the continuous casting covering slag that physics and chemistry or mechanical means evenly mix, mainly bringing into play in continuous casting process: the protection crystallizer molten steel surface is not subjected to air oxidation; To molten steel face adiabatic heat-insulation; Absorb the field trash that floats in the molten steel; In process of billet withdrawal, serve as lubricant; The control strand is to this five big function of heat transfer of crystallizer.Wherein, base-material (mainly contains CaO, SiO
2, Al
2O
3) and flux (Na
2O, F
-, B
2O
3, Li
2O) fusion temperature, viscosity, the absorption of mainly regulating covering slag be mingled with, physical parameter such as crystal property, controlling the performance of the lubricated and uniformly transfer heat function of covering slag; Carbonaceous material (carbon black, graphite, coke etc.) is then being controlled the melting model and the burn-off rate of covering slag; therefore; carbonaceous material can be described as melting rate modifier again, and it crusts, guarantees that to avoiding covering slag melt cinder flows to strand uniformly and stably and the crystallizer wall gap plays important effect at crystallizer molten steel surface.We can say that containing carbonaceous material is the typical composition characteristic that continuous casting covering slag is different from other metallurgical cinder.The mechanism of carbonaceous material control covering slag fusion process is: on the one hand, disperse is distributed in the carbonaceous powder between base-material and the flux mixture powder, each mixture powder particle is kept apart, hinder and delayed the mixture contingent sintering reaction in the temperature-rise period that is heated, can reduce or eliminate the excessively flourishing and slag circle that occurs of crystallizer internal cause sintering; On the other hand, dystectic carbonaceous material is mingled in the mixture slag drop with solid phase particle skeleton form, has slowed down melt cinder and has dripped the speed of assembling the formation molten slag layer.Carbonaceous material just can be controlled the fusion process of covering slag effectively by the comprehensive function of isolation and this two aspect of skeleton.But,, between the covering slag molten slag layer on the crystallizer molten steel surface and not molten sinter layer or fritting layer, usually have the enriched carbon layer of the about 0.1～2mm of a layer thickness because the saturation solubility of carbon in slag is very low.Studies show that even contain 2% the carbon of having an appointment in the covering slag product, the carbon in the enriched carbon layer still can be up to 5～25%.When this covering slag was used for casting the ultra-low-carbon steel of [C]≤50ppm, enriched carbon layer and molten steel or nascent meniscus base shell joint touched, and cause the serious carburetting of strand easily, have reduced continuous casting productivity ratio and product made from steel quality.
For solving the carburetting problem of covering slag to strand, people have carried out big quantity research, and groundwork comprises:
(1) allocates the carbonaceous material that is difficult for strand carburetting in the covering slag into.For example, under the prerequisite that can control the covering slag pre-arcing characterisitics, select the low carbonaceous material of ignition point for use, allow charcoal scaling loss in the covering slag fusion process as much as possible, reduce the enriched carbon layer carbon content; Adopt the big carbonaceous material of specific area to replace the little carbonaceous material of specific area always to join charcoal amount etc. to reduce in the slag.Yet, up to the present, preferably, when the casting ultra-low-carbon steel, still cause casting billet surface carburetting in such covering slag greater than 10ppm.
(2) replace carbonaceous material with nitride.For example, in covering slag, add BN, Si
3N
4, MnN, Ca
2Nitride such as N are controlled the burn-off rate of covering slag to replace carbonaceous material.Particularly BN is similar to crystal structure of graphite, is difficult under strong reducing property atmosphere and covering slag base-material bonding.But, the easy oxidation by air of nitride and generate oxide and nitrogen, B
2O
3This type oxide makes slag fusion temperature and viscosity sharply reduce N
2Be wrapped in and cause slag blanket bubbling and expansion in the slag, this is very harmful to stablizing casting process.For suppressing the generation of this phenomenon, there is the people to propose in covering slag, to add reducing agents such as Al, Si alloy again.But in the actual production, crystallizer protecting residue is in the melted by heat process, and the local chance that contacts with air is a lot, and the effect of said method is also not obvious.And the BN superfines costs an arm and a leg, and about 30～500,000 yuan/ton in China, if with addition of 3%BN, the covering slag cost can raise 9000～15000 yuan/ton, therefore, almost is not applied to suitability for industrialized production with addition of the scheme of nitride.
(3) replace carbonaceous material with carbide.For example, use SiC, WC, CaC
2, TiC, ZrC, Mo
2The all or part of replacement carbon black of carbide such as C or NbC can play and suppress carbon black to the carburetting of strand with reach the purpose of controlling the covering slag burn-off rate.Yet because the action characteristic of these carbide and covering slag base-material, for example the extremely strong wetability of SiC solid particle and slag is wherein easily impelled the rising of covering slag viscosity, has hindered the normal performance of other metallurgical performance of covering slag.
Summary of the invention
The objective of the invention is, provide a kind of and neither influence the metallurgical performance of covering slag itself, can prevent the covering slag of the continuous casting billet carburetting of ultra-low-carbon steel preferably again.
What realize described purpose is a kind of like this protective slag for continuous super low carbon steel casting.The component of this covering slag (weight %) is: 1.41 carbonaceous material, 2.38 metal melting rate modifier, 4.67 MgO, 6.82 Na
2O, 4.76 F
-, 3.89 Al
2O
3, 6.51 MnO, 1.69 Fe
2O
3, all the other are CaO and SiO
2Wherein, CaO/SiO
2Be 1.02.
Further feature is that carbonaceous material wherein is a carbon black.
Further feature is, metal melting rate modifier wherein is any or any two sums or wantonly three kinds of sums or the four kinds of sums in Ca-Si alloy, Ca-Ba-Si alloy, Mn-Si alloy, the Fe-Mn alloy.
From scheme, be not difficult to find out; in covering slag of the present invention; the component ratio of carbonaceous material is very low (is lower than existing low ratio 2%); that is to say; compared with prior art, the present invention directly just reduces the source of continuous casting of ultralow carbon steel base carburetting from the carbonaceous material content aspect of covering slag.Regulate the reasonable volume of material in order not reduce burn-off rate, the present invention used again prior art not such covering slag with the metal melting rate modifier of crossing, have " skeleton isolations " function, come the additional this melting rate modifier of carbonaceous material that has reduced.Simultaneously, the present invention has increased Fe again in covering slag
2O
3, component such as MnO, carbon reaction to allow in they and the enriched carbon layer, further reduce its carbon content.Therefore, compared with prior art, the present invention be with abovementioned technology comprehensively in covering slag, thereby accomplished both to avoid the carburetting of covering slag to continuous casting billet, guaranteed the coordination performance of other every metallurgical functions of covering slag again.
The present invention is further illustrated below in conjunction with accompanying drawing.
Description of drawings
Fig. 1 be in the covering slag content of carbon black to the influence of covering slag sintering exponential sum steel sample carburetting
Fig. 2 is 1350 ℃ of metal melting rate modifiers and the nonwetting state of covering slag slag
Fig. 3 is that the covering slag slag layer thickness is over time in the continuous casting production process
In Fig. 2,1 is the covering slag slag; 2 is the metal melting rate modifier
The specific embodiment
A kind of protective slag for continuous super low carbon steel casting.The component of this covering slag (weight %) is: 0.5～1.6 carbonaceous material, 2～8 metal melting rate modifier, 2～7 MgO, 6～12 Na
2O, 2～8 F
-, 2～7 Al
2O
3, 3～8 MnO, 1～3 Fe
2O
3, all the other are CaO and SiO
2Wherein, CaO/SiO
2Be 0.75～1.05.
In covering slag of the present invention, CaO and SiO
2Be base-material, by their ratio control covering slag basicity.
When the higher Ultra-low carbon electrical sheet of casting [Si] content and since the casting blank shell heat-transfer capability a little less than, for avoiding the bleed-out accident, covering slag basicity CaO/SiO
2Get 0.75～0.85, can guarantee that the slag film is a vitreum, has good lubrication property to strand;
And the no atom gap punching press that contains [Ti] or [Nb] in casting is got basicity CaO/SiO when using steel
2Be 0.85～1.05, help covering slag and absorb crystallizer steel-slag Al at the interface
2O
3, TiO
2Deng field trash, reduce casting billet surface and surface defect, stablize the physical indexs such as setting temperature, viscosity of slag simultaneously, with the high-speed continuous casting of realization stable smooth operation.
Al in the covering slag of the present invention
2O
3And Fe
2O
3, mainly bring in the covering slag by raw material.According to CaO-SiO
2-Al
2O
3Ternary phase diagrams, the Al of certain content
2O
3Help stablizing the physicochemical property of covering slag, as casting Al
2O
3When being mingled with few steel grade, Al in the covering slag
2O
3Content can be controlled in (weight %) 4～7, and casting Al
2O
3When being mingled with more steel grade, Al in the covering slag
2O
3Content should be controlled at (weight %) 2～4.
Add the MgO in this content range in the covering slag of the present invention, main purpose is to stablize the fusion temperature and the viscosity of covering slag.Because when not containing MgO in the covering slag and since float in the molten steel contain CaO, the MgO field trash can reduce covering slag viscosity and rising covering slag fusion temperature, makes the covering slag performance no longer bring out casting blank defect with casting parameters coupling; After containing a certain amount of MgO in the covering slag, effect weakens above-mentioned field trash to the covering slag Effect on Performance, and the covering slag performance tends towards stability.The high-melting-point component is separated out but too high MgO content impels forsterite etc. again easily, worsens the lubrication property of covering slag, so MgO gets (weight %) 2～7 and is advisable.
Na in the covering slag of the present invention
2O and F
-, be used for and CaO and SiO
2The fusion temperature of acting in conjunction control covering slag is that 1070～1150 ℃, 1300 ℃ following viscosity are 0.10～0.35PaS.Because Na
2O self fusing point (920 ℃) is lower, in covering slag with CaO and SiO
2Low melting point eutectic be can form, thereby the fusion temperature of covering slag, F reduced
-Then interrupt complicated silica anion radical structure, make slag micro unit size decreases be easy to migration, reduce covering slag viscosity thus by replacing the bridging oxygen position.The casting speed of determining when continuous casting process is 0.65～1.4m/min, and covering slag fusion temperature and viscosity are got the middle upper limit, Na in above-mentioned scope
2O and F
-Content is value between the middle limit of the present invention regulation and lower limit, and the casting speed of determining when continuous casting process is 1.4～2.0m/min, and covering slag fusion temperature and viscosity are got lower limit in above-mentioned scope, Na
2O and F
-Content is value between the middle limit of the present invention regulation and the upper limit.
In this specific embodiment, used carbonaceous material is a carbon black.Be mainly used in and satisfy carrying out the most basic isolation between the covering slag matrix particulate, the operating characteristic that endangers covering slag to prevent excessive sintering between the covering slag particulate.With phosphorus content be the steel sample fusing of 42ppm respectively in the induction furnace of laboratory after; the covering slag that on the molten steel face, adds different content of carbon black; tested steel sample carbon increasing amount and covering slag sintering agglomerate situation behind the insulation certain hour; the results are shown in Figure 1, thus the result as can be known, content of carbon black surpasses 1.7% in covering slag; easily cause strand carburetting; but content of carbon black is low excessively, and covering slag sintering degree is serious, and the serious conglomeration of covering slag just can't normally be used in continuous cast mold after the sintering index is greater than 1.5.Therefore, covering slag content of carbon black value of the present invention is (weight %) 0.5～1.6.
In this specific embodiment, described metal melting rate modifier is any or any two sum or wantonly three kinds of sums or the four kinds of sums in Ca-Si alloy, Ca-Ba-Si alloy, Mn-Si alloy, the Fe-Mn alloy.Use metal melting rate modifier purpose to be to replace the part carbonaceous material; the fusion process of covering slag is controlled and stablized to metal melting rate modifier performance " isolation skeleton " function; make the covering slag pre-arcing characterisitics can satisfy the continuous casting process requirement; because of metal melting rate modifier carbon containing not, therefore can not cause strand carburetting again.The metal melting rate modifier of covering slag of the present invention descends and covering slag slags nonwetting (angle of wetting is seen Fig. 2 greater than 90 °) at 1250～1350 ℃ after treatment, and this is the basic reason that the metal melting rate modifier can effectively be controlled the covering slag fusion process.
Say that further in described metal melting rate modifier, the molal quantity of each component equates.For example: Ca-Si alloy and Ca-Ba-Si alloy combination, so, in the metal melting rate modifier of this combination, the molal quantity of Ca, Si still equates with the molal quantity of Ba.
In covering slag of the present invention, MnO passes through following formula
MnO+C＝Mn+CO
With the C reaction in the enriched carbon layer, thermodynamics begins 1410 ℃ of reaction temperatures, and this temperature is equivalent to the temperature of enriched carbon layer between molten slag layer and the fritting layer.That is to say; when temperature is lower than 1410 ℃; MnO be difficult for covering slag in the carbonaceous material reaction; like this, in granulated slag or particle slag blanket and sinter layer, carbonaceous material all can be given full play to " skeleton isolation " effect and the fusion process of adjusting covering slag; have only after temperature is higher than 1410 ℃; promptly in enriched carbon layer, molten slag layer, MnO consumes the C oxidation, has avoided the high enriched carbon layer of phosphorus content to strand carburetting.And, since the MnO oxidisability a little less than, after part kish melting rate modifier reaction, can not pollute molten steel and worsen the physical property of covering slag.
Say that further this covering slag is a pre-melted type hollow bead slag, its granularity is 0.1～1.0mm.The concrete making with existing similar; that is: materials such as base-material and flux are melted in premelt furnace-condensation-pulverizing and jevigating after; mix in gyratory agitation device with carbonaceous material and metal melting rate modifier; atomization drying is shaped in spray drying tower, and making granularity is the pre-melted type hollow bead covering slag of 0.1～1.0mm.
In view of those skilled in the art is doing a large amount of work aspect the research of protective slag for continuous super low carbon steel casting, aspect theory and practice, all accumulate a large amount of, rich experience.Therefore; after conscientiously having read this specific embodiment and corresponding analysis the thereof; one surely according to other actual conditions; in the scope of component that the present invention proposes and corresponding proportion thereof; (doing the test of limited several times routine at the most again) select one group of covering slag prescription that satisfies other conditions particularly, realizing the present invention, and reach technique effect of the present invention.So, below only enumerate the checking embodiment an of the best.
This checking embodiment carries out in continuous casting crystallizer for plate billet, and the comparative example 1 of contrast and comparative example 2 are two kinds of existing covering slags.
In the present embodiment, the casting carbon content is smaller or equal to the ultra-low-carbon steel of 50ppm, and casting speed is 0.80～1.40m/min.Be engraved in the strand relevant position and get the steel sample when tundish is got molten steel sample and correspondence, analyze the carbon content in the steel sample, Baogang's sample phosphorus content promptly obtains the strand carbon increasing amount in the middle of being deducted by strand steel sample phosphorus content.Table 1 has provided the chemical composition of embodiment, comparative example 1, comparative example 2 covering slags.Fig. 3 has provided slag layer thickness in covering slag of the present invention and comparative example 1, the comparative example 2 covering slag casting cycles.As shown in Figure 3, after comparative example 1 covering slag adds crystallizer, prolong with casting time, liquid slag layer constantly thickens, and not only covering slag is poor to molten steel face heat insulating ability, and blocked up liquid slag layer influences the accurate control of mould liquid level easily and brings out the bleed-out accident, (casting time of about one heat steel) is forced to drag for slag during therefore to 45min, liquid level is subjected to serious interference like this, and strand carburetting is also serious, is 7～12ppm; Comparative example 2 is owing to contain the higher carbon material, and liquid slag layer thickness is stable in the casting cycle, but liquid slag layer thickness is 5～9mm, this thickness is poor for the continuous casting process adaptive capacity of high pulling rate, it is low by 86.58% that casting billet surface does not have the cleaning rate, and strand carburetting is more, is 8～15ppm; And covering slag of the present invention not only fusion process is stable, slag layer thickness is stabilized in 9～12mm in sequence casting, satisfies the higher continuous casting process condition of casting speed; casting billet surface does not have the cleaning rate and reaches 97.2%; carbon increasing amount is 2～6ppm, average 4.6ppm, and strand all is used for red sending.
Table 1 embodiment and comparative example covering slag chemical composition
Claims (7)
1, a kind of protective slag for continuous super low carbon steel casting is characterized in that, the component of this covering slag (weight %) is: 1.41 carbonaceous material, 2.38 metal melting rate modifier, 4.67 MgO, 6.82 Na
2O, 4.76 F
-, 3.89 Al
2O
3, 6.51 MnO, 1.69 Fe
2O
3, all the other are CaO and SiO
2Wherein, CaO/SiO
2Be 1.02.
2, protective slag for continuous super low carbon steel casting according to claim 1 is characterized in that, described carbonaceous material is a carbon black.
3, protective slag for continuous super low carbon steel casting according to claim 1 and 2; it is characterized in that described metal melting rate modifier is any or any two sum or wantonly three kinds of sums or the four kinds of sums in Ca-Si alloy, Ca-Ba-Si alloy, Mn-Si alloy, the Fe-Mn alloy.
According to the protective slag for continuous super low carbon steel casting described in claim 1 or 2, it is characterized in that 4, this covering slag is a pre-melted type hollow bead slag, its granularity is 0.1～1.0mm.
According to the protective slag for continuous super low carbon steel casting described in the claim 3, it is characterized in that 5, this covering slag is a pre-melted type hollow bead slag, its granularity is 0.1～1.0mm.
According to the protective slag for continuous super low carbon steel casting described in the claim 3, it is characterized in that 6, in described metal melting rate modifier, the molal quantity of each component equates.
According to the protective slag for continuous super low carbon steel casting described in the claim 5, it is characterized in that 7, in described metal melting rate modifier, the molal quantity of each component equates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100950620A CN100443215C (en) | 2006-08-25 | 2006-08-25 | Protective slag for ultralow carbon steel continuous casting |
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|---|---|---|---|
| CNB2006100950620A CN100443215C (en) | 2006-08-25 | 2006-08-25 | Protective slag for ultralow carbon steel continuous casting |
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| CN1911559A CN1911559A (en) | 2007-02-14 |
| CN100443215C true CN100443215C (en) | 2008-12-17 |
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| CN101530896B (en) * | 2008-03-14 | 2011-06-15 | 宝山钢铁股份有限公司 | High casting speed continuous casting covering slag used for ultra-low-carbon steel |
| CN101658907B (en) * | 2009-09-16 | 2013-10-09 | 河南通宇冶材集团有限公司 | Protective slag of large-profile round billet continuous-casting crystallizer and method for preparing same |
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| CN102398003B (en) * | 2010-09-16 | 2015-01-21 | 攀钢集团钢铁钒钛股份有限公司 | Crystallizer covering slag for continuous casting and method for continuously casting medium and low-carbon steel round billets |
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| CN102847897B (en) * | 2012-08-17 | 2015-07-22 | 南京钢铁股份有限公司 | Protecting slag for sulphur-containing free-cutting steel crystallizer and use process |
| CN103042187B (en) * | 2012-12-21 | 2016-01-20 | 江苏大学 | A kind of high-titanium alloy welding wire steel protective slag for continuous casting and preparation method thereof |
| CN104226947B (en) * | 2013-06-17 | 2016-08-17 | 上海梅山钢铁股份有限公司 | A kind of tundish covering flux used for ultra-low-carbon steel |
| CN104646650A (en) * | 2015-02-03 | 2015-05-27 | 舞阳钢铁有限责任公司 | Ultra-low carbon covering slag used for 50t-level large flat ingot die casting |
| KR101857996B1 (en) * | 2016-09-07 | 2018-05-17 | 주식회사 포스코 | Continuous casting method of austenitic stainless steel with improved surface defect |
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| CN1911559A (en) | 2007-02-14 |
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