CN104550797A - Hyporeactive crystallizer casting powder for rear earth steel continuous casting - Google Patents

Hyporeactive crystallizer casting powder for rear earth steel continuous casting Download PDF

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Publication number
CN104550797A
CN104550797A CN201510016163.3A CN201510016163A CN104550797A CN 104550797 A CN104550797 A CN 104550797A CN 201510016163 A CN201510016163 A CN 201510016163A CN 104550797 A CN104550797 A CN 104550797A
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rare earth
sio
activity
continuous casting
cao
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CN104550797B (en
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刘承军
亓捷
姜茂发
刘莹莹
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Northeastern University China
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Northeastern University China
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/11—Treating the molten metal
    • B22D11/111—Treating the molten metal by using protecting powders

Abstract

The invention discloses hyporeactive crystallizer casting powder for rear earth steel continuous casting. The hyporeactive crystallizer casting powder comprises the following components in percentage by weight: 5-20% of Li2O, 5-20% of Ce2O3, 2-10% of SiO2, the balance of CaO and Al2O3, wherein a mass ratio of CaO to Al2O3 is 0.5-1.5, impurities are not more than 10%; the part with grain size of (-)200 meshes accounts for over 80% of the total amount; a melting temperature is 1050-1235 DEG C, and viscosity is 0.15-0.48Pa.s when the melting temperature is 1300 DEG C; surface tension is 0.24-0.53N/m when the melting temperature is 1350 DEG C. The hyporeactive crystallizer casting powder has proper viscosity, surface tension and melting temperature, can be used for effectively restraining reactions between rear earth element and a casting powder group in molten liquid, and improving the continuous-casting crystallization effect of the rear earth steel.

Description

A kind of hypoergia crystallizer protecting residue of rare earth steel continuous casting
Technical field
The invention belongs to metallurgical technology field, particularly a kind of hypoergia crystallizer protecting residue of rare earth steel continuous casting.
Background technology
As everyone knows, rare earth in steel effectively can play cleaning molten steel, going bad is mingled with the effect with microalloying, the application of rare earth in steel is constantly expanded, the kind of rare earth micro alloyed steel and Rare Earth Treated Steel gets more and more, as 09CuPTiRE weathering steel, 310 high-strength weathering Yi shape steels, BNbRE Properties of Heavy Rail Steel, BVRE Properties of Heavy Rail Steel etc., wheel steel etc.Because trace rare-earth significantly can improve the high-temperature oxidation resistance of steel, elevated temperature strength and thermoplasticity, the application of rare earth in heat resisting steel gets more and more, as serial rare-earth heat resisting steel such as S30815, S31060, S34800.Rare earth in molten steel is extremely active, and for ensureing that the content of rare earth reaches steel grades requirement, excessively need add rare earth, the addition scope of rare earth is 0.01% ~ 1.0%.
Continuous crystallizer protecting slag is Powdered or graininess, is one of main steel-making auxiliary material; In casting process, it is covered in above crystallizer molten steel, form slag layer, sinter layer and liquid slag layer from top to bottom, effectively play adiabatic heat-insulation, isolated air prevents molten steel secondary oxidation, absorb field trash in molten steel, lubricate the metallurgical function such as strand and the heat transfer of crystallization control device; Can the metallurgical function of above-mentioned crystallizer protecting residue stablize performance, improves have important impact to continuous casting process direct motion and slab quality.If covering slag performance is bad, very easily cause the blemish such as slag inclusion and crackle, time serious, bleed-out accident can occur.
Conventional continuous crystallizer protecting slag composition is mainly positioned at CaO-Al 2o 3-SiO 2with wollastonite (CaOSiO in ternary system 2) be main low melting point region, CaO is about 30% ~ 50%, SiO 2be 45% ~ 60%, Al 2o 3<20%, fusion temperature is at 1300 ~ 1500 DEG C; In addition, in covering slag base-material, also CaF is added 2, Na 2o, K 2o, Li 2o, B 2o 3, the auxiliary material such as BaO as flux, play the effect of fluxing.Also carbonaceous material is added for regulating the burn-off rate of covering slag.
Conventional continuous crystallizer protecting slag is not also suitable for the casting cycle of rare earth steel; One of reason is, the chemical property of rare earth is active, and the element such as oxygen, sulphur easily and in molten steel forms rare earth oxide or rare earth oxysulfide, and in the casting cycle of rare earth steel, in molten steel, a large amount of dystectic re inclusion floats up to slag gold interface; If covering slag is limited to its absorbent properties; then a large amount of rare earth oxide and rare earth oxysulfide are mingled with and assemble in slag gold interface; and cause the formation of slag bar, slag circle, have a strong impact on the lubrication of covering slag, heat transfer property, thus cause the generation of surface defect of bloom.
The re inclusion assembled due to slag gold interface enters in liquid covering slag; change the physical and chemical performance of continuous casting covering slag; its melting conditions is deteriorated; viscosity increases; cause the slag film between strand and crystallizer thinning, even local is without slag, is deteriorated to the lubricity of strand; thus cause slab surface crack increase, cause the probability of sticker type breakout to increase.
In casting process, the molten steel in crystallizer directly contacts with the covering slag of melting, and because the reproducibility of rare earth is extremely strong, the slag gold interfacial reaction in crystallizer is comparatively serious.Rare earth in molten steel very easily with the SiO in covering slag 2, Na 2the constituent elements such as O react, and the composition of covering slag is changed, and the metallurgical function of covering slag worsens; Therefore, the reactivity reducing rare earth steel continuous crystallizer protecting slag becomes one of problem needing solution badly.
About control continuous cast mold impeller in slurry pump on the impact of covering slag performance, relevant measure proposes in the patents such as JP2005152973, CN200810039377.2, and its solution is for increasing SiO in initial covering slag 2content, after making it interfacial reaction being reduced at generation slag gold, overall composition changing ratio is less; But theory analysis shows, increase initial SiO 2content increases the reaction tendency of rare earth and covering slag constituent element on the contrary, and be unfavorable for the slag gold interfacial reaction suppressed in crystallizer, the method is poor effect when casting rare earth steel.
The patents such as JP2003181606, JP2006110578, CN200710042540.6 of having reported, propose to increase basicity, reduce SiO in initial covering slag 2content, effectively to reduce impeller in slurry pump performance.But still the Na of high level need be added 2o, CaF 2deng flux; Na 2o is SiO comparatively 2rare earth more easily and in molten steel reacts, and increases slag gold interfacial reaction trend; In addition, that adds high level contains F constituent element, easily causes the pollution to water body and air, increases environmental pressure.
Conventional continuous crystallizer protecting slag can not meet the requirement that rare earth steel continuous casting is produced, and the rare earth steel continuous crystallizer protecting slag that exploitation has less reactive and good re inclusion solution absorption performance has important practical significance.
Summary of the invention
For the problems referred to above that existing rare earth steel crystallizer protecting cinder for continuous casting technology exists; the invention provides a kind of hypoergia crystallizer protecting residue of rare earth steel continuous casting; by adjusting the composition of covering slag; make it have suitable viscosity, surface tension and fusion temperature, the effect of rare earth steel continuous casting crystallining can be improved.
The composition of the hypoergia crystallizer protecting residue of rare earth steel continuous casting of the present invention is by weight percentage containing Li 2o 5 ~ 20%, Ce 2o 35 ~ 20%, SiO 22 ~ 10%, all the other are CaO and Al 2o 3, and CaO and Al 2o 3mass ratio be 0.5 ~ 1.5, granularity accounts for total amount more than 80% in-200 object parts.
The fusion temperature of the hypoergia crystallizer protecting residue of above-mentioned rare earth steel continuous casting is 1050 ~ 1235 DEG C, and viscosity when 1300 DEG C is 0.15 ~ 0.48 Pas, and surface tension when 1350 DEG C is 0.24 ~ 0.53N/m.
The hypoergia crystallizer protecting residue of above-mentioned rare earth steel continuous casting 1450 DEG C time, SiO in slag system 2activity be 3.56 × 10 -5~ 1.56 × 10 -3, Ce 2o 3activity be 2.50 × 10 -3~ 7.29 × 10 -2; 1500 DEG C time, SiO in slag system 2activity be 2.77 × 10 -5~ 1.9 × 10 -3, Ce 2o 3activity be 3.51 × 10 -3~ 9.37 × 10 -2.
The preparation method of the hypoergia crystallizer protecting residue of rare earth steel continuous casting of the present invention is:
Prepare CaO, Al 2o 3, SiO 2, Li 2cO 3and Ce 2(CO 3) 3as raw material, Li 2cO 3consumption press Li 2o counts, Ce 2(CO 3) 3consumption press Ce 2o 3meter; By DEG C high temperature fritting of whole heating raw materials to 1400 ± 10, Li 2cO 3be decomposed into Li 2o, Ce 2(CO 3) 3be decomposed into Ce 2o 3, then shrend, then drying and dehydrating, then sieve, and obtains the hypoergia crystallizer protecting residue of rare earth steel continuous casting.
The hypoergia crystallizer protecting residue of rare earth steel continuous casting of the present invention effectively can suppress the impeller in slurry pump of casting process, and the principle of its Composition Design is:
For ensureing that crystallizer protecting residue has between suitable liquid phase region, according to CaO-Al 2o 3phasor, when w(CaO)/ w(Al 2o 3) when being about 0.94, there is low melting point 12CaO7Al 2o 3phase; CaO-Al is drawn according to utilizing thermodynamic software Factsage 2o 3-SiO 2isollaothermic chart, at high calcium high alumina still there is low melting point region in district, this region using the one-tenth component selections reference area as slag system of the present invention, to reduce its reactivity worth; From above two figure, w(SiO 2) <10%, w(CaO)/ w(Al 2o 3) ≈ 0.5 ~ 1.5 time, there is low-melting-point material phase or low melting point region; Therefore the present invention drafts w(CaO)/ w(Al 2o 3) scope be 0.5 ~ 1.5;
Li 2o is the main fluxing of slag system of the present invention, has report to point out, Li 2o content often increases by 1%, and fusion temperature reduces by 60 DEG C, and in slag system of the present invention, it mainly plays the effect reducing covering slag fusion temperature and viscosity; Because slag system of the present invention does not add comparatively Li 2o is more easily by Na that molten steel rare earth elements reduces 2o, K 2the CaF of O and non-environment-friendly type 2deng flux, therefore, Li 2the addition of O increases; By Li 2o-Al 2o 3phasor is known, at Li 2o and Al 2o 3when mass ratio is about 1, there is low melting point region, therefore, slag system of the present invention, with reference to this composition, is made suitable adjustment to slag system composition, is worked as Li 2it is comparatively suitable when O addition is 5 ~ 20%; Further, Li 2o replaces by the lithium carbonate resource of cheapness, obtained in fritting decomposable process;
Ce 2o 3for suppressing one of major components of slag gold interfacial reaction in slag system of the present invention, being added the activity that can increase product, thus effectively being suppressed the molten steel rare earth elements shown in following formula and the reaction between covering slag constituent element; And, according to CaO-AlO 1.5-CeO 1.5system Feo-feo figure, Ce 2o 3scope be defined as 5 ~ 20%, relatively stable to ensure that slag system of the present invention absorbs property retention after rare earth oxide.
Reaction equation between above-mentioned molten steel rare earth elements and covering slag constituent element is:
2 x[RE]+ y（SiO 2）= y[Si]+2（RE xO y）
；
In formula, with be respectively the activity of [Si] and [RE] in molten steel; with be respectively SiO in slag 2and RE xo yactivity.
Thermodynamic software Factsage is utilized to calculate the activity of related components in covering slag, SiO in the hypoergia crystallizer protecting residue of rare earth steel continuous casting 2there is lower activity, Ce 2o 3there is higher activity; This slag system has lower reactivity.
Accompanying drawing explanation
Fig. 1 is the response curve of common constituent element in molten steel rare earth elements and covering slag;
Fig. 2 is CaO-Al 2o 3phasor;
Fig. 3 is the CaO-Al utilizing thermodynamic software Factsage to draw 2o 3-SiO 2the isollaothermic chart of system;
Fig. 4 is Li 2o-Al 2o 3the phasor of system;
Fig. 5 is CaO-AlO 1.5-CeO 1.5the liquid phase interval graph of system; In figure, L is between liquid phase region.
Detailed description of the invention
The material purity adopted in the embodiment of the present invention all >=99%.
Viscosity and surface tension employing high-temperature fusant physical property comprehensive tester (adopting rotating cylinder method and hollow cylinder method respectively) is tested in the embodiment of the present invention.
Testing fusing point in the embodiment of the present invention adopts fusing point to melt fast analyzer (half ball).
Thermodynamic software Factsage is adopted to calculate the activity of related components in covering slag in the embodiment of the present invention.
Embodiment 1
The composition of the hypoergia crystallizer protecting residue of rare earth steel continuous casting is by weight percentage containing Li 2o 10%, Ce 2o 310%, SiO 210%, all the other are CaO and Al 2o 3, and CaO and Al 2o 3mass ratio be 0.5, granularity accounts for total amount more than 80% in-200 object parts; Fusion temperature is 1176 DEG C, and viscosity when 1300 DEG C is 0.32 Pas, and surface tension when 1350 DEG C is 0.32N/m; 1450 DEG C time, SiO in slag system 2activity be 1.56 × 10 -3, Ce 2o 3activity be 2.50 × 10 -3; 1500 DEG C time, SiO in slag system 2activity be 1.90 × 10 -3, Ce 2o 3activity be 3.15 × 10 -3;
Preparation method is: prepare CaO, Al 2o 3, SiO 2, Li 2cO 3and Ce 2(CO 3) 3as raw material, Li 2cO 3consumption press Li 2o counts, Ce 2(CO 3) 3consumption press Ce 2o 3meter; By DEG C high temperature fritting of whole heating raw materials to 1400 ± 10, Li 2cO 3be decomposed into Li 2o, Ce 2(CO 3) 3be decomposed into Ce 2o 3, then shrend, then drying and dehydrating, then sieve.
Embodiment 2
The composition of the hypoergia crystallizer protecting residue of rare earth steel continuous casting is by weight percentage containing Li 2o 10%, Ce 2o 315%, SiO 23%, all the other are CaO and Al 2o 3, and CaO and Al 2o 3mass ratio be 1.5, granularity accounts for total amount more than 80% in-200 object parts; Fusion temperature is 1223 DEG C, and viscosity when 1300 DEG C is 0.36 Pas, and surface tension when 1350 DEG C is 0.53N/m; 1450 DEG C time, SiO in slag system 2activity be 3.56 × 10 -5~ 6.24 × 10 -4, Ce 2o 3activity be 7.29 × 10 -2; 1500 DEG C time, SiO in slag system 2activity be 2.77 × 10 -5, Ce 2o 3activity be 9.37 × 10 -2;
Preparation method is with embodiment 1.
Embodiment 3
The composition of the hypoergia crystallizer protecting residue of rare earth steel continuous casting is by weight percentage containing Li 2o 15%, Ce 2o 35%, SiO 26%, all the other are CaO and Al 2o 3, and CaO and Al 2o 3mass ratio be 1.0, granularity accounts for total amount more than 80% in-200 object parts; Fusion temperature is 1105 DEG C, and viscosity when 1300 DEG C is 0.26 Pas, and surface tension when 1350 DEG C is 0.24N/m; 1450 DEG C time, SiO in slag system 2activity be 3.51 × 10 -4, Ce 2o 3activity be 8.30 × 10 -3; 1500 DEG C time, SiO in slag system 2activity be 4.54 × 10 -4, Ce 2o 3activity be 9.76 × 10 -3;
Preparation method is with embodiment 1.
Embodiment 4
The composition of the hypoergia crystallizer protecting residue of rare earth steel continuous casting is by weight percentage containing Li 2o 5%, Ce 2o 320%, SiO 22%, all the other are CaO and Al 2o 3, and CaO and Al 2o 3mass ratio be 0.8, granularity accounts for total amount more than 80% in-200 object parts; Fusion temperature is 1235 DEG C, and viscosity when 1300 DEG C is 0.46 Pas, and surface tension when 1350 DEG C is 0.36N/m; 1450 DEG C time, SiO in slag system 2activity be 1.66 × 10 -4, Ce 2o 3activity be 9.70 × 10 -3; 1500 DEG C time, SiO in slag system 2activity be 1.76 × 10 -4, Ce 2o 3activity be 1.28 × 10 -2;
Preparation method is with embodiment 1.
Embodiment 5
The composition of the hypoergia crystallizer protecting residue of rare earth steel continuous casting is by weight percentage containing Li 2o 20%, Ce 2o 35%, SiO 210%, all the other are CaO and Al 2o 3, and CaO and Al 2o 3mass ratio be 1.2, granularity accounts for total amount more than 80% in-200 object parts; Fusion temperature is 1050 DEG C, and viscosity when 1300 DEG C is 0.15 Pas, and surface tension when 1350 DEG C is 0.51N/m; 1450 DEG C time, SiO in slag system 2activity be 9.77 × 10 -4, Ce 2o 3activity be 6.23 × 10 -3; 1500 DEG C time, SiO in slag system 2activity be 9.77 × 10 -4, Ce 2o 3activity be 6.15 × 10 -3;
Preparation method is with embodiment 1.
Embodiment 6
The composition of the hypoergia crystallizer protecting residue of rare earth steel continuous casting is by weight percentage containing Li 2o 10%, Ce 2o 315%, SiO 25%, all the other are CaO and Al 2o 3, and CaO and Al 2o 3mass ratio be 0.9, granularity accounts for total amount more than 80% in-200 object parts; Fusion temperature is 1176 DEG C, and viscosity when 1300 DEG C is 0.48 Pas, and surface tension when 1350 DEG C is 0.36N/m; 1450 DEG C time, SiO in slag system 2activity be 3.51 × 10 -4, Ce 2o 3activity be 8.30 × 10 -3; 1500 DEG C time, SiO in slag system 2activity be 4.22 × 10 -4, Ce 2o 3activity be 1.00 × 10 -2;
Preparation method is with embodiment 1.

Claims (4)

1. a hypoergia crystallizer protecting residue for rare earth steel continuous casting, is characterized in that composition by weight percentage containing Li 2o 5 ~ 20%, Ce 2o 35 ~ 20%, SiO 22 ~ 10%, all the other are CaO and Al 2o 3, and CaO and Al 2o 3mass ratio be 0.5 ~ 1.5, impurity≤10%; Granularity accounts for total amount more than 80% in-200 object parts.
2. the hypoergia crystallizer protecting residue of a kind of rare earth steel continuous casting according to claim 1; it is characterized in that the fusion temperature of this crystallizer protecting residue is 1050 ~ 1235 DEG C; viscosity when 1300 DEG C is 0.15 ~ 0.48 Pas, and surface tension when 1350 DEG C is 0.24 ~ 0.53N/m.
3. the hypoergia crystallizer protecting residue of a kind of rare earth steel continuous casting according to claim 1, is characterized in that this crystallizer protecting residue is 1450 DEG C time, SiO in slag system 2activity be 3.56 × 10 -5~ 1.56 × 10 -3, Ce 2o 3activity be 2.50 × 10 -3~ 7.29 × 10 -2; 1500 DEG C time, SiO in slag system 2activity be 2.77 × 10 -5~ 1.9 × 10 -3, Ce 2o 3activity be 3.51 × 10 -3~ 9.37 × 10 -2.
4. a preparation method for the hypoergia crystallizer protecting residue of rare earth steel continuous casting according to claim 1, is characterized in that: prepare CaO, Al 2o 3, SiO 2, Li 2cO 3and Ce 2(CO 3) 3as raw material, Li 2cO 3consumption press Li 2o counts, Ce 2(CO 3) 3consumption press Ce 2o 3meter; By DEG C high temperature fritting of whole heating raw materials to 1400 ± 10, Li 2cO 3be decomposed into Li 2o, Ce 2(CO 3) 3be decomposed into Ce 2o 3, then shrend, then drying and dehydrating, then sieve, and obtains the hypoergia crystallizer protecting residue of rare earth steel continuous casting.
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN105834383A (en) * 2016-06-16 2016-08-10 东北大学 Casting powder for aluminate series crystallizer for rare earth heat resistant steel continuous casting and preparing method of casting powder
CN106041006A (en) * 2016-08-10 2016-10-26 中南大学 Continuous casting tundish covering agent of Mn-containing and Al-containing steel and application thereof
CN110614351A (en) * 2019-10-30 2019-12-27 江苏理工学院 Continuous casting covering slag for stainless steel and preparation method thereof
CN113857448A (en) * 2021-11-29 2021-12-31 东北大学 Low-alkalinity coating-free protective slag for continuous casting of hot forming steel
CN114029462A (en) * 2021-11-15 2022-02-11 东北大学 Rare earth oxide-containing continuous casting mold flux for high-titanium low-aluminum steel and preparation method thereof
CN115026249A (en) * 2022-05-23 2022-09-09 首钢京唐钢铁联合有限责任公司 Covering slag for producing sheet billet high-drawing-speed low-carbon steel and preparation method thereof

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CN103128240A (en) * 2011-11-28 2013-06-05 上海梅山钢铁股份有限公司 Low carbon steel continuous casting crystallizer casting powder
CN103308547A (en) * 2013-05-27 2013-09-18 内蒙古包钢钢联股份有限公司 Method for judging dissolving property of crystallizer casting slag to rare earth oxide

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Publication number Priority date Publication date Assignee Title
CN105834383A (en) * 2016-06-16 2016-08-10 东北大学 Casting powder for aluminate series crystallizer for rare earth heat resistant steel continuous casting and preparing method of casting powder
CN106041006A (en) * 2016-08-10 2016-10-26 中南大学 Continuous casting tundish covering agent of Mn-containing and Al-containing steel and application thereof
CN110614351A (en) * 2019-10-30 2019-12-27 江苏理工学院 Continuous casting covering slag for stainless steel and preparation method thereof
CN110614351B (en) * 2019-10-30 2021-05-18 江苏理工学院 Continuous casting covering slag for stainless steel and preparation method thereof
CN114029462A (en) * 2021-11-15 2022-02-11 东北大学 Rare earth oxide-containing continuous casting mold flux for high-titanium low-aluminum steel and preparation method thereof
CN113857448A (en) * 2021-11-29 2021-12-31 东北大学 Low-alkalinity coating-free protective slag for continuous casting of hot forming steel
CN113857448B (en) * 2021-11-29 2022-02-22 东北大学 Low-alkalinity coating-free protective slag for continuous casting of hot forming steel
CN115026249A (en) * 2022-05-23 2022-09-09 首钢京唐钢铁联合有限责任公司 Covering slag for producing sheet billet high-drawing-speed low-carbon steel and preparation method thereof
CN115026249B (en) * 2022-05-23 2024-02-09 首钢京唐钢铁联合有限责任公司 Covering slag for producing low-carbon steel with high pulling speed of sheet billet and preparation method thereof

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