CN107297475B - A kind of high alumina steel continuous casting crystallizer Mold Powder Without Fluorine - Google Patents
A kind of high alumina steel continuous casting crystallizer Mold Powder Without Fluorine Download PDFInfo
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- CN107297475B CN107297475B CN201710518289.XA CN201710518289A CN107297475B CN 107297475 B CN107297475 B CN 107297475B CN 201710518289 A CN201710518289 A CN 201710518289A CN 107297475 B CN107297475 B CN 107297475B
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- sio
- fluorine
- mold powder
- slag
- covering slag
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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 present invention relates to a kind of high alumina steel continuous casting crystallizer Mold Powder Without Fluorines；The covering slag is made of the oxide component of following mass percentage content: CaO 30%~45%, SiO210%~25%, Al2O320%~35%, MgO 2%~10%, B2O34%~10%, (Na2O+Li2O) 8%~15%, 1.1≤CaO/ (SiO2+Al2O3)≤1.3,3.5≤CaO/B2O3≤ 7,1≤SiO2/B2O3≤1.7.Such covering slag slag steel extent of reaction is lower, and crystal property is good, and Crystalline Phase is mainly calcium borosilicate.The calcium borosilicate of formation is capable of fixing the SiO in covering slag melt2, therefore reacted from it is weakened in kinetics with Al element in steel, greatly improve covering slag stability；And calcium borosilicate crystal can efficiently control the heat-transfer effect of covering slag.
Description
Technical field
The invention belongs to smelting iron and steel continuous-casting arts, are related to a kind of good high-aluminum steel Mold Powder Without Fluorine of physicochemical property.
Background technique
Continuous crystallizer protecting slag has in continuous casting process prevents oxidation, absorption are mingled with, lubricate green shell and Heat Transfer Control
Etc. numerous critical functions, wherein mostly important with lubrication and heat transmission function, it is to raising cc billet surface quality and guarantees continuous casting
It goes on smoothly and plays an important role.Al in the continuous casting process of high-aluminum steel, molten steel can enter in two different ways to be protected
It protects in slag, one is being rapidly absorbed into covering slag in the form of nonmetallic oxide inclusion, oxygen preferentially in conjunction with Al, generates gold
Belong to oxide to be mingled with；Another kind be by with SiO in covering slag2React (4 [Al]+3 (SiO2(the Al of)=22O3)+3[Si])
Into in covering slag, SiO in covering slag2Consumption will cause the basicity (CaO/SiO of covering slag2) sharply increase, Al2O3Content
It dramatically increases, so that the penalties such as the viscosity of covering slag, fusing, crystallization and heat transfer, transmit unstable and profit so as to cause heat
Cunning is insufficient, and steel billet is finally made the serious surface defect such as crack and recess occur.
In addition, in general, in addition to CaO, SiO in the component of continuous crystallizer protecting slag2、Al2O3Except equal base-materials, also need to add
Enter CaF2、Li2O、Na2The fluxing agents such as O.Wherein, fluorine can reduce the viscosity, fusion temperature and setting temperature of covering slag significantly, have
Effect ground promotes the heat transfer property of Solidified Flux Film crystallization control covering slag；And fluoride is resourceful, cheap.Therefore, become
Continuous crystallizer protecting slag common substance.It is asked however, fluorine-containing covering slag will cause following three aspects in continuous casting process
Topic: 1) fluorine can react and generate harmful fluoride (HF, the SiF of low melting point in covering slag fusion process4, NaF etc.), and cause
The corrosion of equipment and the damage of worker's health；2) in cyclic process with and Cold Water Exposure, fluorine, which can be discharged into water, to be caused
Water sample causes the pollution of water body and the corrosion of equipment in acidity；3) in used waste residue stacking process, fluorine can be also discharged into
The pollution of soil and groundwater is caused in soil.
As the development of Chinese national economy and comprehensive unlatching of 13 construction, steel industry face product structure tune
Whole test, advanced high-strength steel (AHSS) such as TRIP, TWIP steel because of the light weight the features such as better than the performance of orthodox car steel due to
As research hotspot in recent years；On the other hand due to the worsening of environment, to the brought environmental pollution of Ferrous Metallurgy process
The concern of problem is also increasingly paid attention to.Therefore, the research of continuous crystallizer protecting slag fluoride-free is very necessary and urgent.And
The matter of utmost importance of high-aluminum steel continuous crystallizer protecting slag fluoride-free reduces the progress of slag steel reaction, while guaranteeing the physics and chemistry of covering slag
Performance can meet practical continuous casting.
Summary of the invention
It is an object of that present invention to provide a kind of physicochemical property, good and slag steel reacts less high-aluminum steel Mold Powder Without Fluorine, allows
Covering slag slag steel after fluoride-free reacts less and lubricant effect and crystal property etc. all in the normal range, to guarantee to solidification
The effective control conducted heat in the process.
To achieve the above object, the technical scheme is that
A kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, is made of the oxide of following mass percentage:
CaO 30%~45%, preferably 39.5~44.5%；
SiO210%~25%, preferably 10~12%；Further preferably 10%；
Al2O320%~35%, preferably 22~28.5%；
MgO 2%~10%,
B2O34%~10%, preferably 6~10%；
(Na2O+Li2O) 8%~15%,
CaO and B2O3Mass ratio be 3.5~7:1；
SiO2With B2O3Mass ratio be 1~1.7:1.
Preferably, CaO and B2O3Mass ratio be 3.95~7:1.
Preferably, SiO2With B2O3Mass ratio be 1~1.25:1.
A kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, passes through strict control SiO2/B2O3And SiO2/B2O3Ratio promotes borosilicate
The formation of sour calcium crystal, the formation of calcium borosilicate have the SiO being conducive in fixed covering slag melt2, thus in kinetics
Weaken it to react with Al element in steel, greatly improves covering slag stability.
A kind of high-aluminum steel Mold Powder Without Fluorine of the present invention contains calcium borosilicate crystal in crystalline phase, and the calcium borosilicate is brilliant
The percent crystallization in massecuite of body is 70%~95%
A kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, the molten temperature region of the high-aluminum steel Mold Powder Without Fluorine are 1050 DEG C
Between~1160 DEG C.
A kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, at 1300 DEG C of the high-aluminum steel Mold Powder Without Fluorine viscosity be 0.07~
0.16Pa·s.Covering slag has good mobility and lubricity.
A kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, the crystallization temperature of the high-aluminum steel Mold Powder Without Fluorine is 1260 DEG C~
1310 DEG C, the crystallization incubation time is 15s~28s.
A kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, the mean heat flux of the high-aluminum steel Mold Powder Without Fluorine is 0.58~
0.75MW/m2。
A kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, Li2The mass percentage of O is no more than 3%.
Preferably, CaO/ (SiO in the medium carbon steel Mold Powder Without Fluorine2+Al2O3) it is 1.10~1.30.
Preferably, a kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, by the oxide group of following mass percentage
At: CaO 41.90%, SiO210%, Al2O328.10%, MgO 2%, Na2O 10%, Li2O 2%, B2O36%.
Preferably, a kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, by the oxide group of following mass percentage
At: CaO 40.86%, SiO210%, Al2O327.14%, MgO 2%, Na2O 10%, Li2O 2%, B2O38%.
Preferably, a kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, by the oxide group of following mass percentage
At: CaO 39.81%, SiO210%, Al2O326.19%, MgO 2%, Na2O 10%, Li2O 2%, B2O310%.
Preferably, a kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, by the oxide group of following mass percentage
At: CaO 42.55%, SiO210%, Al2O325.45%, MgO 2%, Na2O 10%, Li2O 2%, B2O38%.
Preferably, a kind of high-aluminum steel Mold Powder Without Fluorine of the present invention, by the oxide group of following mass percentage
At: CaO 44.09%, SiO210%, Al2O323.91%, MgO 2%, Na2O 10%, Li2O 2%, B2O38%.
High alumina steel continuous casting crystallizer Mold Powder Without Fluorine according to the present invention, preparation method is as follows, by above-mentioned protection
According to target ingredient weighs slag raw material, carries out mechanical stirring, so that each ingredient uniformly mixes, then will be mixed using intermediate frequency furnace
Sample is melted in 1500 DEG C of heating afterwards, is removed volatile matter and gaseous matter, complicated solid solution is formed between each component, by molten state
Slag is poured into water chilling and obtains glassy state covering slag block, obtains required guarantor after covering slag block progress Mechanical Crushing is milled
Protect ground-slag body.
Principle and advantage
Covering slag of the invention passes through control CaO/B2O3、SiO2/B2O3Mass ratio, 3.5≤CaO/B2O3≤ 7 and 1≤
SiO2/B2O3≤ 1.7 (especially 1≤SiO2/B2O3≤ 1.25), under the synergistic effect of other appropriate amount of components, borosilicate can be promoted
The formation of the formation of sour calcium crystal, calcium borosilicate can fix the SiO in melt protecting slag2, reduce its in steel Al it is anti-
It answers, to stabilize the physicochemical property of covering slag；The pollution problem of fluorine is avoided simultaneously.
The protection slag melting point that the present invention is developed is low, component collocation is reasonable, avoids the precipitation of the high melting crystals such as nepheline
And then reduce the appearance of the glass properties situation of slag film.
In addition to this, the viscosity of the developed high-aluminum steel Mold Powder Without Fluorine of the present invention is appropriate, this not only contributes to raising slag and exists
Lubricant effect when use；It is also beneficial to the SiO being formed by the fixed melt protecting slag of calcium borosilicate crystal simultaneously2, in turn
Reduce SiO in covering slag melt2It is reacted with [Al] in molten steel, is controlled the reaction of slag steel, to solve high-aluminum steel
The problem of serious slag steel reacts in continuous casting process.
Compared with prior art, present invention has the advantage that
1, Mold Powder Without Fluorine of the invention, is suitable for high-aluminum steel casting powder for continuously casting crystallizer, every physicochemical property and
Parameter, such as fusing point, viscosity, crystallization temperature and heat flow density are close with the fluorine-containing covering slag of tradition.
2, Mold Powder Without Fluorine of the invention, completely solves the fluoride pollution problem in continuous casting process, while the covering slag
Using the corrosion rate for the processing cost and casting machine that can substantially reduce continuous casting cooling water, it can significantly improve the place of recirculated water
Manage pressure and cost.
3, Mold Powder Without Fluorine of the invention, Crystalline Phase are mainly calcium borosilicate (Ca11Si4B2O22).The Crystalline Phase
Generate the SiO be conducive in fixed covering slag2, SiO2The slag steel significant reaction of participation is reduced.The slag solves high-aluminum steel continuous casting mistake
The problem of serious slag steel of journey reacts；And heat transfer control is stablized, and greasy property and meltdown property show well.
Specific embodiment:
The invention will be further elaborated with reference to embodiments, and embodiment is merely to illustrate the present invention, rather than with
Any form limits the present invention.
Embodiment 1
Ingredient: ternary basicity CaO/ (SiO2+Al2O3) it is 1.10, CaO 41.90wt.%, SiO210wt.%, Al2O3
28.10wt.%, MgO 2wt.%, Na2O 10wt.%, Li2O 2wt.%, B2O36wt.%.
Preparation process: by above-mentioned covering slag raw material, according to target ingredient is weighed, and mechanical stirring is carried out, so that each ingredient uniformly mixes
It closes, sample heating fusing after then being mixed using intermediate frequency furnace is removed volatile matter and gaseous matter, formed between each component multiple
Molten state slag is poured into water chilling and obtains glassy state covering slag block by miscellaneous solid solution, covering slag block is carried out mechanical broken
It is broken mill after obtain required covering slag powder.
The main physical index of covering slag is shown in Table 1.
Embodiment 2
Ingredient: ternary basicity CaO/ (SiO2+Al2O3) it is 1.10, CaO 40.86wt.%, SiO210wt.%, Al2O3
27.14wt.%, MgO 2wt.%, Na2O 10wt.%, Li2O 2wt.%, B2O38wt.%.
Preparation process: with embodiment 1.
The main physical index of covering slag is shown in Table 1.
Embodiment 3
Ingredient: ternary basicity CaO/ (SiO2+Al2O3) it is 1.10, CaO 39.81wt.%, SiO210wt.%, Al2O3
26.19wt.%, MgO 2wt.%, Na2O 10wt.%, Li2O 2wt.%, B2O310wt.%.
Preparation process: with embodiment 1.
The main physical index of covering slag is shown in Table 1.
Embodiment 4
Ingredient: ternary basicity CaO/ (SiO2+Al2O3) it is 1.20, CaO 42.55wt.%, SiO210wt.%, Al2O3
25.45wt.%, MgO 2wt.%, Na2O 10wt.%, Li2O 2wt.%, B2O38wt.%.
Preparation process: with embodiment 1.
The main physical index of covering slag is shown in Table 1.
Embodiment 5
Ingredient: ternary basicity CaO/ (SiO2+Al2O3) it is 1.30, CaO 44.09wt.%, SiO210wt.%, Al2O3
23.91wt.%, MgO 2wt.%, Na2O 10wt.%, Li2O 2wt.%, B2O38wt.%.
Preparation process: with embodiment 1.
The main physical index of covering slag is shown in Table 1.
Comparative example 1
Ingredient: ternary basicity CaO/ (SiO2+Al2O3) it is 1.25, CaO 43.33wt.%, SiO229.67wt.%,
Al2O35wt.%, MgO 2wt.%, Na2O 10wt.%, Li2O 2wt.%, B2O38wt.%.
Preparation process: with embodiment 1.
The main physical index of covering slag is shown in Table 1.
Comparative example 2
Ingredient: ternary basicity CaO/ (SiO2+Al2O3) it is 1.25, CaO 46.67wt.%, SiO232.33wt.%,
Al2O35wt.%, MgO3wt.%, Na2O 10wt.%, Li2O 2wt.%, B2O33wt.%.
Preparation process: with embodiment 1.
The main physical index of covering slag is shown in Table 1.
Comparative example 3
Ternary basicity CaO/ (SiO2+Al2O3) it is 1.19, CaO 41.90wt.%, SiO27wt.%, Al2O3
28.10wt.%, MgO7.5wt.%., Na2O 10wt.%, Li2O 2wt.%, B2O33.5wt.%,
Preparation process: with embodiment 1.
The main physical index of covering slag is shown in Table 1.
The main physical index of 1. covering slag of table
High-aluminum steel Mold Powder Without Fluorine of the invention is a kind of high alumina boracic covering slag, every service performance and parameter, such as
The performances such as fusing point, viscosity, crystallization temperature and heat flow density and parameter are able to satisfy the demand of practical continuous casting process technological parameter.
From the point of view of the experimental result of embodiment and comparative example 1,2, embodiment all indicators are better than comparative examples；More important is slag steel
Significant reaction is weaker than comparative example, and embodiment is suitable with 3 slag-metal reaction degree of comparative example, but percent crystallization in massecuite greatly improves, heat flow density
It significantly reduces, is conducive to the control in continuous casting process to steel billet solidified structure.Meanwhile the preferred solution of the invention (such as embodiment 3)
After implementation, gained performance is also much since (such as melting region is narrow, percent crystallization in massecuite superelevation, incubation time for other of the invention products
It is short, mean heat flux is low), this point is well beyond estimated before testing.Therefore it is tight not only to avoid high-aluminum steel by the present invention
The problems such as slag steel reaction of weight, also solve the problem of crystal property and greasy property deteriorate after covering slag fluoride-free.The present invention
Covering slag is especially suitable for high-aluminum steel continuous casting process slag.
Claims (1)
1. a kind of high-aluminum steel Mold Powder Without Fluorine, it is characterised in that；It is made of the oxide of following mass percentage:
CaO 39.81%, SiO210%, Al2O326.19%, MgO 2%, Na2O 10%, Li2O 2%, B2O310%；
Calcium borosilicate crystal is formed in the high-aluminum steel Mold Powder Without Fluorine, and the percent crystallization in massecuite of the calcium borosilicate crystal is 94%;
The molten temperature region of the high-aluminum steel Mold Powder Without Fluorine is between 1067 DEG C ~ 1090 DEG C；
Viscosity is 0.08 ± 0.05 Pa s at 1300 DEG C of the high-aluminum steel Mold Powder Without Fluorine；
The crystallization temperature of the high-aluminum steel Mold Powder Without Fluorine is 1267 ± 5 DEG C, and the crystallization incubation time is 16 s;
The mean heat flux of the high-aluminum steel Mold Powder Without Fluorine is 0.59 MW/m2。
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| CN113751681B (en) * | 2021-09-14 | 2023-06-16 | 鞍钢股份有限公司 | Continuous casting powder suitable for high titanium steel |
| CN114054698B (en) * | 2021-11-10 | 2022-11-01 | 北京科技大学 | Fluoride-free environment-friendly continuous casting mold flux for ultrahigh aluminum steel |
| CN114130972A (en) * | 2021-11-15 | 2022-03-04 | 上海应用技术大学 | Fluoride-free high-aluminum steel continuous casting crystallizer non-reactive covering slag |
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