CN104107890B - A kind of cold rolled sheet steel continuous casting covering slag and manufacture method thereof - Google Patents
A kind of cold rolled sheet steel continuous casting covering slag and manufacture method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of cold rolled sheet steel continuous casting covering slag, and its chemical composition mass percentage content is, Na2O:3��8%; MgO:3��12%; Al2O3: 3��12%; Li2O��3%; F��5%; MnO��15%; BaO��8%; TiO2�� 8%; C:1��3%; All the other are CaO, SiO2With inevitable impurity, wherein CaO/SiO2It is 0.8��1.3. Correspondingly, the invention also discloses the manufacture method of this cold rolled sheet steel continuous casting covering slag. Surface tension after cold rolled sheet steel continuous casting covering slag melting of the present invention can reach 450��550mN/m, increase substantially the not wetting property between slag and molten steel, reducing the probability that covering slag is torn by molten steel and be involved in, also can float fast even if being involved in molten steel; Greatly reduce the possibility that covering slag is caught by molten steel and form subsurface inclusion; Avoid being formed steel defect in follow-up cold rolling step, thus improve the lumber recovery of steel finished product.
Description
Technical field
The present invention relates to a kind of slag material, particularly relate to a kind of steel-making covering slag.
Background technology
The thickness of the steel grade trimmed size such as auto sheet and silicon steel is general all at below 1mm, belongs to a kind of cold rolling shaping thin plate class steel grade. The steel defect that thin plate class steel grade produces in cold-rolled process mainly due to covering slag class be mingled with, Al2O3Be mingled with bubble caused by. Wherein, covering slag class is mingled with and accounts for more than the 60% of this kind of steel defect.
Continuous casting covering slag is the steel-making subsidiary material of a kind of powder shape or fine granularity; its molten steel surface being covered in conticaster crystallizer in molten steel solidification process; under the high temperature action of molten steel, covering slag forms solid liquid two layers, and that layer of adjacent molten steel is melting layer; with to prevent the secondary oxidation of molten steel; slag layer above melting layer, slag layer due to molten steel across melting layer, still remain its virgin state; play good adiabatic heat-insulation effect, to prevent molten steel surface solidifies. Melting layer, under the effect of crystallizer periodic vibration, can flow into again the relative movement to lubricate between initial solidification shell and copper coin between the gap of copper plate of crystallizer and molten steel initial solidification shell continuously, thus ensure that strand has good surface quality; In addition; melting layer also possesses the nonmetal inclusion of floating, the effect of purify hot metal in absorption molten steel; the flux film thickness flowed between copper plate of crystallizer and initial solidification shell gap is generally only 1��2mm; the side of close copper coin is solid phase; the side of close initial solidification shell is still liquid phase; the flux film energy lubricate of liquid phase; the flux film of solid phase then can well crystallization control device copper coin to the cooling power of initial solidification shell; thus regulate the rate of cooling of molten steel, it is used for reaching the effect of Heat Transfer Control. Therefore, covering slag is last one Technology of steelmaking process control cc billet surface quality, is ensure that continuous casting process carries out and the important means of strand workpiece surface quality smoothly. But, owing to molten steel is the flow state of certain rule in continuous cast mold, unavoidably there is relative flowing in its surface. Under the effect of this kind of shear flow, once melt cinder is torn by molten steel, just it is easy to be taken to by molten steel the solidified front of initial solidification shell, and then is caught the subsurface inclusion forming steel grade. After casting blank solidification in the follow-up operation of rolling, subsurface inclusion finally can be exposed to surface of steel plate and form steel defect owing to rolling into thin plate.
Usual covering slag is with CaO, SiO2Binary is main, and is equipped with CaF outward2��Na2O��Li2The fusing assistants such as O, its main function reduces CaO, SiO2The fusing point of two component system and viscosity, in addition, be also furnished with other a small amount of units such as group such as grade as required, thus reach suitable metallurgical performance. Owing to the fusing point of covering slag is low compared to the temperature of molten steel, the covering slag in order to control relative low melting point can slowly melt at molten steel surface and form stable melting layer and slag layer, can add a certain amount of carbonaceous material.
Publication No. is CN102019384A, announcing day is on April 20th, 2011, name is called that the Chinese patent literature of " the high viscosity continuous casting covering slag solving surface of low-carbon steel folder slag " discloses a kind of high viscosity continuous casting covering slag solving surface of low-carbon steel folder slag, the mass percentage of its chemical composition is: glass powder: 0%��7%, pre-melt: 50%��70%, fluorite: 5.5%��8.5%, white alkali: 4%��8%, N330 carbon black: 3%, graphite: 3.5%, R agent: 0%��3%, Quilonum Retard: 0.5%��2%, manganous carbonate: 2%��5%, magnesia: 2%��5%, aluminium vanadine: 3%��7%, sodium aluminum fluoride: 1%��3%, tackiness agent: 1%��3%, water reducer: 0.3%��1%. this continuous casting covering slag is mainly at CaO, SiO2Basis on, the carbonaceous materials such as fusing assistant and certain carbon black, graphite such as additional a certain amount of Quilonum Retard, fluorite or white alkali.
Publication number is JP2008238221, and publication date is on October 9th, 2008, and name is called that the Japanese documentation of " continuous casting covering slag " provides the covering slag of a kind of even casting, and the mass percentage content of the chemical composition of continuous casting covering slag is: SiO2: 5.0��35.0%, Al2O3: 5.0��35.0%, T CaO��40%, NaO:3.0��15.0%, F:2.0��10.0%, MgO��2.5%, surplus composition��20% and T CaO/SiO2It is 0.15 to 1.05, it is 6��30 at 1300 DEG C and equilibrium viscosity under the solidification value of��1260 DEG C. By adding, high-melting-point substances improves viscosity to this technical scheme, but adds the physicals that high-melting-point substances can change covering slag.
Publication number is KR20030054762; publication date is on July 2nd, 2003; name is called that the Korean Patent document of " covering slag for the manufacture of ultralow carbon cold-rolled steel plate " relates to a kind of covering slag for pole low-carbon cold rolling steel plate, and the mass percentage content of its chemical element is: CaO25��40%, SiO225��40%, Al2O31��6%, Na2O2��5%, F5��10%, selects the C of interpolation 1��5%, the Cr of 3��7%2O3, and balance the content between iron and inevitable impurity, and wherein, basicity CaO/SiO2Ratio be 0.95��1.15. The surface tension of covering slag disclosed in patent document in normality situation is 350��450mN/m.
Summary of the invention
It is an object of the invention to provide a kind of cold rolled sheet steel continuous casting covering slag; the surface tension of this covering slag under high temperature fused state can reach 450mN/m; can avoid covering slag in use by the generation of molten steel drag to maximum degree; even and if this covering slag also can floating upward quickly after being involved in by molten steel; thus prevent covering slag from forming subsurface inclusion in molten steel; and then reduce the steel defect of cold rolled sheet steel, it is to increase the finished product recovery rate of slab.
In order to realize foregoing invention object, the present invention proposes a kind of cold rolled sheet steel continuous casting covering slag, its chemical composition mass percentage content is:
Na2O3��8%;
MgO3��12%;
Al2O33��12%;
Li2O��3%;
F��5%;
MnO��15%;
BaO��8%;
TiO2�� 8%;
C1��3%;
All the other are CaO, SiO2With inevitable impurity, wherein CaO/SiO2It is 0.8��1.3.
Cold rolled sheet steel continuous casting covering slag of the present invention, at conventional CaO, SiO2On the basis of two component system, with the addition of a certain amount of F, Na2O��Li2The fusing assistants such as O and MgO, MnO, BaO, Al2O3��TiO2Deng other component.
In addition, in covering slag, inevitably there is the impurity of certain content, it is preferable that control this foreign matter content��3%.
In cold rolled sheet steel continuous casting covering slag of the present invention, the principle of design of each chemical composition is as follows:
CaO and SiO2: in covering slag melt, Ca is with Ca2+Ionic species exists, and it is the positive ion that a kind of electrostatic potential is bigger, to O2-The reactive force of ion is stronger; Si is then with (SiO4)4-Composite negative ion form exist, it to bath surface thus can be reduced the surface tension of covering slag melt by exclusion. In order to improve the surface tension of slag, the CaO content added is more high more good, the SiO added2Content is more low more good. But, CaO and SiO2Being form the most basic chemistry composition of covering slag, in order to ensure the normal performance of the every physical and chemical performance of covering slag, the basicity of this cold rolled sheet steel required by continuous casting covering slag must control within certain limit, i.e. CaO/SiO2Ratio; When basicity is lower than 0.8, slag surface tension force obviously reduces; When basicity is higher than 1.3; the physical indexs such as covering slag fusing point, analysis crystalline substance are too high, are not only unfavorable for the fusing of covering slag, are also unfavorable for that melt cinder plays lubrication between copper plate of crystallizer and the gap of initial solidification shell; therefore, basicity should be controlled between 0.8��1.3 in the present invention.
Na2O: in covering slag melt, Na+Electrostatic potential less, for strengthening the effect of covering slag surface tension and little. But Na2O is a kind of fusing assistant the most common in covering slag, it is possible to effectively reduce fusing point and the viscosity of covering slag. In addition, Na2The existence of O can promote sodium rankinite (Na2O��CaO��SiO2) and nepheline (Na2O��Al2O3��2SiO2) etc. crystal precipitate out, contribute to covering slag play Heat Transfer Control effect. In order to ensure that it plays fluxing action, usual added mass percentage content is not less than 3%, but due to Na+Raising covering slag surface tension effects is very limited, and its mass percentage content should control below 8%.
MgO:Mg2+It is the positive ion that a kind of electrostatic potential is bigger, the effect strengthening covering slag surface tension is bigger. But, along with the raising of content of MgO in covering slag, the brilliant proneness of slag analysis also raises gradually, merwinite (3CaO MgO 2SiO2), bredigite (7CaO MgO 4SiO2) and akermanite (2CaO MgO 2SiO2) it is comparatively common crystal habit. When the mass percentage of MgO is greater than 12%, the precipitation intensity of crystal is excessive, is unfavorable for that melt cinder plays its lubrication like this. Therefore, in technical solution of the present invention, the mass percentage content of MgO is set as 3��12%.
Al2O3: Al3+To O2-Reactive force relatively big, it is conducive to improving the surface tension of covering slag. Meanwhile, Al2O3Being again the organizer of network structure in covering slag melt, its existence can improve the viscosity of covering slag, reduces the amount of precipitation of crystal, is the important chemical composition regulating Slag Properties. But, when its mass percentage content is more than 12%, Al2O3The impact of covering slag viscosity is excessive, it is unfavorable for the lubrication of strand.
Li2O: although Li+Electrostatic potential also relatively little, but Li2O can obviously reduce fusing point and the viscosity of covering slag, is also a kind of very effective fusing assistant. Due to Li2O is expensive, and excessive interpolation can significantly improve the production cost of covering slag, therefore, as the auxiliary fusing assistant of one, and Li2O suitably can add when fusing point, viscosity are higher, and comprehensive cost factor is considered, Li2The interpolation mass percentage content of O is no more than 3%.
F:F can break Si-O chain-like structure in the melt to reduce the viscosity of slag significantly, and F or cuspidite (3CaO 2SiO2��CaF2) necessary composition, so F is component indispensable in covering slag. But, F-Electrostatic potential very low, it is easy to be ostracised slag surface and reduce surface tension. Comprehensive every factor is considered, should F mass percentage content be controlled within 5%.
MnO:Mn2+Also being the positive ion that a kind of electrostatic potential is bigger, MnO can improve the surface tension of covering slag effectively. But, MnO, as a kind of transition element oxide compound, easily replaces MgO in crystalline structure or coexists formation composite crystal with MgO, therefore its add-on can not be too high. Due to MnO and SiO2Belonging to the component that oxygen gesture is higher in covering slag, in use with the Al in steel, redox reaction can occur, thus reduce the actual content of MnO in slag, therefore, its mass percentage content added should control within 15%.
BaO:BaO and CaO is all alkaline earth metal oxide, adds BaO and can reach the effect improving surface tension and slag basicity equally, and the impact of analysis crystalline substance is weaker than CaO by BaO, is also component comparatively common in multicomponent covering slag. Its density is bigger than normal, adds excessive easily making covering slag face the uneven risk of fusing, therefore the mass percentage content of BaO is set as��8%.
TiO2: Ti4+With Si4+Mutually similar, it is easy to form composite negative ion and arrived bath surface by exclusion, thus reduces the surface tension of covering slag. But, TiO2Have and be beneficial to the viscosity for covering slag and the analysis physical property such as crystalline substance carries out comprehensive adjustment, so it is also a kind of important component of covering slag. In the cold rolled sheet steel continuous casting covering slag of the present invention, its mass percentage content is controlled within 8%.
C: owing to covering slag fusing point is lower than liquid steel temperature about 400 DEG C; in order to Control protection slag at molten steel surface stably fused and keeps certain slag layer thickness (being as the criterion to play the effect of adiabatic heat-insulation), it is necessary to add appropriate carbonaceous material in covering slag. Because carbon is a kind of high-melting-point substances, can prevent the covering slag melted from forming small droplets and assemble; In addition, become gas after carbon burning also can not be polluted by covering slag. Although carbon is a kind of ideal additive, but covering slag can be suppressed to form necessary melting layer excessive adding, therefore the mass percentage content of C be controlled 1��3%.
Correspondingly, present invention also offers the manufacture method of this cold rolled sheet steel continuous casting covering slag, comprising:
(1) mix after raw material being worn into fine powder;
(2) above-mentioned fine powder is carried out fritting, obtain Solid solution;
(3) again grind after broken for Solid solution cooling, obtain pre-melt fine powder;
(4) in pre-melt fine powder, add the fine powder described in step (1) and allocate carbonaceous material into, so that composition meets requirement;
(5) granulate.
Further, in the manufacture method of above-mentioned cold rolled sheet steel continuous casting covering slag, described pre-melt fine powder accounts for massfraction >=50% of covering slag total amount.
Further, in the manufacture method of above-mentioned cold rolled sheet steel continuous casting covering slag, the particle diameter of described pre-melt fine powder is less than 0.075mm.
Further, in the manufacture method of above-mentioned cold rolled sheet steel continuous casting covering slag, described carbonaceous material comprises carbon black and/or graphite.
Further, granulated by mechanically mixing in described step (5), or adopt spray drying device to granulate.
In the technical program; in order to ensure that covering slag is fast, evenly melt; after above-mentioned covering slag raw material mixes by respective component proportion; need first to carry out fritting process to make between each chemical composition, to form complicated heterogeneous Solid solution; thus make the molten temperature region of covering slag, it is about to fusing end of a period temperature and melts beginning temperature difference control within a narrower scope. Covering slag after fritting can adjust accordingly according to composition deviation, and the ratio of the pre-melted slag used preferably is not less than 50%. The melt that covering slag after fusing is made up of many oxide and fluorochemical, oxygen element and fluorine element are with O2-��F-Negative ion form exist, other element then exists mainly with independent ion mode greatly. Surface tension is relevant with the existence form of these elements, due to O2-Radius ratio positive ion radius is big, therefore when covering slag turns into melt, melt cinder surface is mainly by O2-Occupied by, positive ion is to O2-Reactive force more big, the surface tension that melt shows is more big.
When the melt cinder temperature after the cold rolled sheet steel continuous casting covering slag melting of the present invention reaches 1300 DEG C, its surface tension can reach 450��550mN/m, has increased substantially the not wetting property between slag and molten steel; Reduce the probability that covering slag is torn and be involved in molten steel by molten steel shear flow, even and if covering slag also can float fast after being involved in molten steel; Greatly reduce the possibility that covering slag is caught by molten steel and form steel plate subsurface inclusion; Avoid being formed steel defect in follow-up cold rolling step, thus improve the lumber recovery of steel finished product.
Embodiment
Come below in conjunction with specific embodiments to carry out cold rolled sheet steel continuous casting covering slag of the present invention illustrating in detail further, but this explanation does not form the improper restriction for technical solution of the present invention.
Embodiment 1-6 and comparative example 1-2
Cold rolled sheet steel continuous casting covering slag is manufactured according to the following step:
(1) raw material needed for covering slag being worn into fine powder and Homogeneous phase mixing, wherein raw material includes but not limited to: Wingdale, quartz, wollastonite, magnesia, bauxitic clay, fluorite, sodium aluminum fluoride, glass, barium carbonate, soda ash, manganous carbonate, pigment manganese, Quilonum Retard, lithium concentrate and titanium ore:
(2) carry out fritting and form Solid solution, with obtain burn-off rate faster evenly pre-melt;
(3) by broken for the cooling of pre-melt, the pre-melt fine powder that particle diameter is less than 0.075mm is ground to form;
(4) raw material fine powder is adopted to finely tune according to composition deviation, and add appropriate carbonaceous material (such as carbon black or graphite), wherein pre-melt fine powder accounts for the ratio >=50wt% of covering slag, and the mass percentage content of each chemical composition of Control protection slag is as shown in table 1;
(5) granule type finished product is obtained by mechanically mixing or by spraying dry.
Each chemical composition mass percentage content (%, surplus is inevitable impurity) of the covering slag of table 1. embodiment 1-6 and comparative example 1-2
| Chemical composition | Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Na2O | 3 | 8 | 5 | 6 | 5 | 3 | 8 | 4 |
| MgO | 4.5 | 6 | 11 | 7 | 9 | 5 | 10 | 3 |
| Al2O3 | 4.5 | 5 | 3 | 12 | 8 | 6 | 9 | 5 |
| Li2O | --- | --- | --- | --- | 2 | 1 | 0.5 | 2.5 |
| F | 6.7 | 5 | 2 | 5 | --- | --- | 3 | 4 |
| MnO | --- | --- | 5 | 10 | 14 | 3 | 8 | --- |
| BaO | --- | --- | 7 | 4 | 6 | 3 | --- | 2 |
| TiO2 | --- | --- | 4 | --- | 2 | 6 | 8 | --- |
| C | 2.1 | 1.5 | 1.2 | 2.0 | 1.6 | 2.5 | 2.2 | 1.8 |
| CaO | 37.5 | 33.5 | 27.5 | 29 | 25.5 | 36 | 24 | 42 |
| SiO2 | 39.5 | 38.5 | 32.5 | 23 | 25.5 | 33 | 26 | 35 |
| CaO/SiO2 | 0.95 | 0.87 | 0.85 | 1.26 | 1.0 | 1.1 | 0.92 | 1.2 |
The covering slag that table 2 shows embodiment 1-6 and comparative example 1-2 surface tension in the molten state and steel strand covering slag folder slag incidence.
Table 2
| Sequence number | Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Surface tension | 420 | 380 | 475 | 520 | 545 | 490 | 500 | 460 |
| (mN/m) | ||||||||
| Folder slag incidence | Higher | High | Lower | Low | Low | Low | Low | Lower |
As known from Table 2, the surface tension of the cold rolled sheet steel continuous casting covering slag in embodiment 1-6 can reach more than 460mN/m, all higher than the surface tension of covering slag of comparative example 1-2; Meanwhile, compared to the steel strand of the covering slag adopting comparative example 1-2, the dreg defect incidence of the steel strand covering slag of the cold rolled sheet steel continuous casting covering slag in embodiment 1-6 is adopted obviously to reduce.
The cold rolled sheet steel continuous casting covering slag of the present invention is 450��550mN/m the melt cinder surface tension of 1300 DEG C; not only can reduce the probability that melt cinder is involved in by molten steel; even if melt cinder also can float rapidly after being mixed into molten steel; thus largely avoided the possibility that covering slag forms dreg defect at strand and cause it finally to become steel and be mingled with; improve the lumber recovery of steel finished product, it is particularly useful for the manufacturing of cold rolled sheet steel.
That enumerates it is noted that above is only specific embodiments of the invention, it is clear that the invention is not restricted to above embodiment, has many similar changes thereupon. If all distortion that the technician of this area directly derives from content disclosed by the invention or associates, protection scope of the present invention all should be belonged to.
Claims (8)
1. a cold rolled sheet steel continuous casting covering slag, it is characterised in that, its chemical composition mass percentage content is:
All the other are CaO, SiO2With inevitable impurity, wherein CaO/SiO2It is 0.8��1.3;
The surface tension of described cold rolled sheet steel continuous casting covering slag under high temperature fused state is more than 450mN/m.
2. cold rolled sheet steel continuous casting covering slag as claimed in claim 1, it is characterised in that, inevitable impurity mass percentage��3%.
3. the manufacture method of cold rolled sheet steel continuous casting covering slag as claimed in claim 1 or 2, it is characterised in that, comprising:
(1) mix after raw material being worn into fine powder;
(2) above-mentioned fine powder is carried out fritting, obtain Solid solution;
(3) again grind after broken for Solid solution cooling, obtain pre-melt fine powder;
(4) in pre-melt fine powder, add the fine powder described in step (1) and allocate carbonaceous material into, so that composition meets requirement;
(5) granulate.
4. the manufacture method of cold rolled sheet steel continuous casting covering slag as claimed in claim 3, it is characterised in that, described pre-melt fine powder accounts for massfraction >=50% of covering slag total amount.
5. the manufacture method of cold rolled sheet steel continuous casting covering slag as claimed in claim 3, it is characterised in that, the particle diameter of pre-melt fine powder is less than 0.075mm.
6. the manufacture method of cold rolled sheet steel continuous casting covering slag as claimed in claim 3, it is characterised in that, described carbonaceous material comprises carbon black and/or graphite.
7. the manufacture method of cold rolled sheet steel continuous casting covering slag as claimed in claim 3, it is characterised in that, described step is granulated by mechanically mixing in (5).
8. the manufacture method of cold rolled sheet steel continuous casting covering slag as claimed in claim 3, it is characterised in that, described step (5) adopt spray drying device granulate.
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| CN104607608B (en) * | 2015-01-29 | 2017-02-22 | 中南大学 | Medium manganese steel casting powder for automobile and application thereof |
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| CN107498012B (en) * | 2017-06-29 | 2019-11-01 | 中南大学 | One kind TRIP steel covering slag of high alumina containing BaO and its application |
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| CN109732048B (en) * | 2019-03-28 | 2021-05-04 | 西峡龙成冶金材料有限公司 | Covering slag for automobile plate steel continuous casting crystallizer, preparation method and application thereof |
| CN110605365B (en) * | 2019-09-29 | 2021-06-01 | 河南通宇冶材集团有限公司 | Manganese-containing pre-melted material, casting powder containing pre-melted material and application of casting powder |
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| CN112705678B (en) * | 2020-12-16 | 2022-04-08 | 西峡龙成冶金材料有限公司 | Continuous casting crystallizer covering slag for hot work die steel slab and application thereof |
| CN114082909A (en) * | 2021-10-22 | 2022-02-25 | 邯郸钢铁集团有限责任公司 | Continuous casting mold flux for low-alloy high-strength beam steel |
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