CN101519747A - Rare-earth aluminum-calcium-iron alloy - Google Patents
Rare-earth aluminum-calcium-iron alloy Download PDFInfo
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- CN101519747A CN101519747A CN200910118978A CN200910118978A CN101519747A CN 101519747 A CN101519747 A CN 101519747A CN 200910118978 A CN200910118978 A CN 200910118978A CN 200910118978 A CN200910118978 A CN 200910118978A CN 101519747 A CN101519747 A CN 101519747A
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Abstract
The invention discloses a rare-earth aluminum-calcium-iron alloy which can denature inclusions in steel, produce high-clearness steel plates and particularly improve the smelting technology of low-carbon and low-silicon plates with high drawability so as to satisfy the requirements of high-grade automobiles, household electrical appliances, and the like for the performance of the steel plates. The alloy comprises the following ingredients by weight: 30-60 percent of Al, 1-10 percent of Ca, 1-20 percent of RE, 0-0.08 percent of C, 0-0.5 percent of Si, 0-0.03 percent of S, 0-0.03 percent of P, 0.001-1 percent of unavoidable impurity element gross and the rest percent of iron. The RE is a misch metal containing Ce or/and La, and the gross of the Ce and the La in the misch metal is 90-100 -percent of the gross of the RE.
Description
Technical field
The present invention relates to a kind of rare-earth aluminum-calcium-iron alloy, belong to the ferrous metallurgy field.
Background technology
In the process of smelting iron and steel, in order to guarantee the cleaning of molten steel, must remove impurity such as carbon in the molten steel, oxygen, could improve the quality of steel, deoxidation in steel making is mainly finished with the interpolation reductor.Reductor is mainly aluminium, but secondary oxidation and produce Al simultaneously easily
2O
3Be mingled with and influence the performance of steel, need in follow-up operation, effectively be removed.
In order to remove effectively owing to a large amount of aluminium adds the aluminum oxide deoxidation products that generates, the way of mainly taking at present is: (1) prolongs the vacuum stirring time, promotes inclusion floating.But this method will inevitably prolong refining time, increases production cost and reduces output.(2) the slag agent of adding certain ingredients in the vacuum molten bath behind the aluminium deoxidation, this slag agent main component is CaO, its effect is to adsorb the aluminate that floats to the molten steel surface from molten steel effectively.The deficiency of this method is: after adding the slag agent, not only can cause the molten steel temperature loss, melting these slag agent simultaneously also needs 2～3 fens clock times; In addition, can not cause these slag agent to be involved in molten steel yet, molten steel be formed phenomenons such as pollution in case the adding method is appropriate.(3) aluminate is carried out sex change.As: in molten steel, add calcium constituent, make that aluminate especially forms as 12CaO7Al in conjunction with forming the calcium aluminium composite oxide in the steel
2O
3This low melting point large inclusions, this inclusion be come-up removal from molten steel easily on the one hand, because its fusing point is lower, is not easy to cause nozzle clogging at casting process on the other hand, guarantees the cast direct motion.But because therefore calcium metal gasification easily under the steel-making temperature is not easy to add, recovery rate is very low.
Except calcium can make the aluminate sex change, in recent years, both at home and abroad rare earth is attached great importance in the modification and the metamorphism of steel inclusion.But from the prior art, the content of rare earth alloy middle-weight rare earths lower (0.03～1wt%), not enough so that the Al that produces
2O
3Inclusion modification.Perhaps in alloy, do not add useful calcium constituent, can not get the ideal effect at the aspect of performance that improves steel.
Summary of the invention
The purpose of this invention is to provide a kind of rare-earth aluminum-calcium-iron alloy, it can make the inclusion modification in the steel, produces the high-cleanness, high steel, and the low carbon low silicon sheet material smelting technology of high deep drawability is improved.Thereby satisfy the performance requriements to used steel plate such as high-grade automobile, household electrical appliances.
Another object of the present invention provides the preparation method of above-mentioned alloy.
Rare-earth aluminum-calcium-iron alloy of the present invention, its composition and content thereof are: Al 30～60wt%, Ca 1～10wt%, RE 1～20wt%, C 0～0.08wt%, Si 0～0.5wt%, S 0～0.03wt%, P 0～0.03wt%, inevitable impurity element total amount 0.001～1wt%, surplus is an iron.
RE in the rare-earth aluminum-calcium-iron alloy of the present invention is for for containing a kind of mishmetal among Ce, the La at least, and the total content of Ce, La accounts for 90～100wt% of total rare earth content in mishmetal.
The principal feature of this alloy is: (1) adopts the principle of rare earth, aluminium, calcium multielement complex deoxidization, has significantly improved the deoxidation efficient of alloy to molten steel; (2) the formed complex inclusion of deoxidation floats in molten steel easily; (3) form the low melting point inclusion easily, overcome because aluminum oxide too much causes the nozzle clogging phenomenon in the casting process; (4) iron in the alloy, rare earth element have significantly increased alloy proportion, make can enter molten steel fast in the interpolation process, have improved the deoxidation and the inclusion modification effect of aluminium, calcium, rare earth, have improved the utilising efficiency of alloying constituent; (5) solved that calcium in the deep drawing steel RH refining process is handled and the difficult problem of rare earth interpolation aspect; (6) contain the impurity element such as carbon, silicon of utmost point low levels, can not cause carburetting, increase the deficiency of silicon aspect molten steel; (7) adding method is simple, convenient, is difficult for efflorescence, and the shelf time is long.
This product especially is fit to high-quality low-carbon (LC), low silicon, and the sheet material with good deep drawability uses in smelting, and especially the application in RH smelting suprelow carbon steel process has more its uniqueness.
The preparation method of this alloy: utilize fine aluminium ingot, rare earth, calcium metal and low-carbon (LC) high-quality steel scrap to prepare satisfactory finished product alloy by induction furnace two-step approach melting technology.
Basic technology is: be fusing of prepared using induction furnace and the rare-earth aluminum-calcium initial alloy that is mixed with out certain ingredients with fine aluminium ingot, rare earth, calcium metal at first, this is the first step.And then utilize high-quality steel scrap and aluminium ingot in induction furnace, to be smelted into the ferro-aluminum mother liquor for raw material, be added on the initial rare-earth aluminum-calcium alloy that has prepared in the above-mentioned the first step again, and uniform mixing reaches ultimate constituent requirement in induction furnace, enters product library after casting, the cooling then.
Embodiment
The invention is further illustrated by the following examples.
Carry out the deoxidation experiment according to rare-earth aluminum-calcium-iron alloy provided by the invention in actual molten steel, experiment is finished on 20 kilograms of vacuum induction furnaces.
Experimental technique is as follows: (carbon content is 0.03～0.05wt%) to select certain ingredients high-quality steel scrap for use, at first under atmospheric condition, melt and finish, carrying out vacuum decarburization then handles, after carbon content is less than 0.005wt%, vacuum breaker is skimmed, and the oxygen level of measuring in the steel is 0.025～0.040wt%, again vacuumize then, molten steel is remained under the vacuum condition.Under this condition, add different-alloy (ferro-aluminum, aluminium calcium iron, rare-earth aluminum-calcium iron) and carry out deoxidation and alloying, after having added, utilize induction to stir 3 minutes, aluminium content and total oxygen content and with electron microscopic observation inclusion size and quantity in the sampling analysis steel under vacuum, relatively these three kinds of different deoxidization techniques are to the influence of molten steel cleanness.All three kinds of alloying constituents add calculating according to same aluminium addition, and the theoretical add-on of aluminium is 0.10% (recovery rate of aluminium is calculated by 100%).
Different-alloy deoxidation effect contrast composition (wt%) is as shown in the table.
| Numbering | Add initial dissolution oxygen in the preceding steel of alloy | T.O (final sampling, total oxygen content) | Al(s) | Al(t) | Ca | RE | The inclusion type | Maximum inclusion size (μ m) | The amount of inclusions (〉=3 μ m) |
| 1-alloy of the present invention | 0.028 | 0.0080 | 0.050 | 0.058 | 0.0012 | 0.0015 | (Ca, RE, Al) xOy, a small amount of Al 2O 3 | 10 | 50/mm 2 |
| 2-alloy of the present invention | 0.033 | 0.0095 | 0.045 | 0.056 | 0.0008 | 0.0010 | (Ca, RE, Al) xOy, a small amount of Al 2O 3 | 8 | 68/mm 2 |
| 3 alloys of the present invention | 0.039 | 0.0120 | 0.030 | 0.045 | 0.0008 | 0.0005 | (Ca, RE, Al) xOy, a small amount of Al 2O 3 | 13 | 90/mm 2 |
| 4-alloy of the present invention | 0.025 | 0.0070 | 0.057 | 0.063 | 0.0011 | 0.0016 | (Ca, RE, Al) xOy, a small amount of Al 2O 3 | 5 | 43/mm 2 |
| On average (alloy of the present invention) | 0.031 | 0.0091 | 0.046 | 0.056 | 0.0010 | 0.0012 | (Ca, RE, Al) xOy, a small amount of Al 2O 3 | 9 | 63/mm 2 |
| 1-comparative alloy A | 0.022 | 0.0085 | 0.049 | 0.060 | Al 2O 3 | 11 | 70/mm 2 | ||
| 2-comparative alloy A | 0.029 | 0.0090 | 0.042 | 0.052 | Al 2O 3 | 11 | 68/mm 2 | ||
| 3-comparative alloy A | 0.035 | 0.0113 | 0.033 | 0.046 | Al 2O 3 | 15 | 85/mm 2 | ||
| 4-comparative alloy A | 0.037 | 0.0130 | 0.028 | 0.043 | Al 2O 3 | 21 | 110/mm 2 | ||
| On average (comparative alloy A) | 0.031 | 0.0105 | 0.038 | 0.050 | 15 | 83/mm 2 | |||
| 1-comparative alloy B | 0.032 | 0.0098 | 0.034 | 0.043 | 0.0005 | (Ca, Al) xOy, small part Al 2O 3 | 10 | 73/mm 2 | |
| 2-comparative alloy B | 0.028 | 0.0091 | 0.045 | 0.053 | 0.0012 | (Ca, Al) xOy, small part Al 2O 3 | 9 | 60/mm 2 | |
| 3-comparative alloy B | 0.026 | 0.0090 | 0.044 | 0.055 | 0.0011 | (Ca, Al) xOy, small part Al 2O 3 | 8 | 65/mm 2 | |
| 4-comparative alloy B | 0.040 | 0.0118 | 0.033 | 0.050 | 0.0005 | (Ca, Al) xOy, small part Al 2O 3 | 12 | 88/mm 2 | |
| On average (comparative alloy B) | 0.032 | 0.0099 | 0.039 | 0.050 | 0.0008 | 10 | 72/mm 2 |
In the table: comparative alloy A-refer to and the identical ferroaluminium of alloy aluminum content of the present invention;
Comparative alloy B-refer to and alloy aluminum of the present invention, the Al-Ca-Fe alloy that calcium contents is identical;
T.O-refer to entire oxygen content in the steel content;
Al (s), Al (t), Ca, the chemical analysis content of RE-refer to respectively sour molten aluminium in the steel, full aluminium, calcium, rare earth;
(Ca, RE, Al)
xO
yInclusion-refer to that the inclusion of being found contains Ca under the condition under electron microscope, RE, the composite oxides that the Al element is formed, subscript x, y refer to that concrete composition of inclusions has the unified signal expression formula of multiple uncertain type;
(Ca, Al)
xO
yInclusion-refer to that the inclusion of being found only contains Ca under the condition under electron microscope, the Al element, and do not contain the composite oxides that the RE element is formed;
From last table experimental result contrast as can be seen, new alloy of the present invention is under the approaching condition of average initial oxygen content, the aluminium that adds equal amts, can play the recovery rate that improves aluminium, reduce oxygen level, make the inclusion modification and remove the high advantage of efficient, also have certain residual Re amount in the molten steel simultaneously.Therefore rare-earth aluminum-calcium alloy proposed by the invention is to the high-cleanness, high steel, and the improvement of the low carbon low silicon sheet material smelting technology of especially high deep drawability is significant.
Claims (2)
1, a kind of rare-earth aluminum-calcium-iron alloy, it is characterized in that, the composition of this alloy and content thereof are: Al 30～60wt%, Ca 1～10wt%, RE 1～20wt%, C 0～0.08wt%, Si 0～0.5wt%, S 0～0.03wt%, P 0～0.03wt%, inevitable impurity element total amount 0.001～1wt%, surplus is an iron.
2, rare-earth aluminum-calcium-iron alloy according to claim 1 is characterized in that, described RE is a kind of mishmetal that contains among Ce, the La at least, and the total content of Ce, La accounts for 90～100wt% of total rare earth content in mishmetal.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181606A (en) * | 2011-04-08 | 2011-09-14 | 包头市北科创业高新材料有限责任公司 | Rare earth aluminum manganese calcium iron alloy and production method thereof |
| CN102766801A (en) * | 2012-08-16 | 2012-11-07 | 包头市北科创业高新材料有限责任公司 | Rare earth Al-Ca-Fe alloy for rare earth micro-treated steel and preparation method thereof |
| CN104164622A (en) * | 2014-08-13 | 2014-11-26 | 无棣向上机械设计服务有限公司 | Low-alloy steel metal material and manufacturing method thereof |
| CN104805337A (en) * | 2015-05-18 | 2015-07-29 | 北京科技大学 | Rear-earth aluminum, silicom and calcium ferroalloy and preparation method of rear-earth aluminum, silicom and calcium ferroalloy |
| CN106834602A (en) * | 2016-12-16 | 2017-06-13 | 包头稀土研究院 | Steel-making rare-earth aluminum-calcium ferrosilicon composite alloy and preparation method thereof |
| CN107881369A (en) * | 2017-10-27 | 2018-04-06 | 大唐东北电力试验研究所有限公司 | Aluminium calcium antimony intermediate alloy inovulant and preparation method thereof |
| CN109778060A (en) * | 2019-03-26 | 2019-05-21 | 内蒙古锦和稀土功能材料有限公司 | Rare earth alloy and its preparation method and application |
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2009
- 2009-03-11 CN CN200910118978A patent/CN101519747A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181606A (en) * | 2011-04-08 | 2011-09-14 | 包头市北科创业高新材料有限责任公司 | Rare earth aluminum manganese calcium iron alloy and production method thereof |
| CN102181606B (en) * | 2011-04-08 | 2013-01-23 | 包头市北科创业高新材料有限责任公司 | Production method of rare earth aluminum manganese calcium iron alloy |
| CN102766801A (en) * | 2012-08-16 | 2012-11-07 | 包头市北科创业高新材料有限责任公司 | Rare earth Al-Ca-Fe alloy for rare earth micro-treated steel and preparation method thereof |
| CN104164622A (en) * | 2014-08-13 | 2014-11-26 | 无棣向上机械设计服务有限公司 | Low-alloy steel metal material and manufacturing method thereof |
| CN104164622B (en) * | 2014-08-13 | 2016-08-24 | 无棣向上机械设计服务有限公司 | A kind of low-alloy steel metal material and preparation method thereof |
| CN104805337A (en) * | 2015-05-18 | 2015-07-29 | 北京科技大学 | Rear-earth aluminum, silicom and calcium ferroalloy and preparation method of rear-earth aluminum, silicom and calcium ferroalloy |
| CN106834602A (en) * | 2016-12-16 | 2017-06-13 | 包头稀土研究院 | Steel-making rare-earth aluminum-calcium ferrosilicon composite alloy and preparation method thereof |
| CN113106198A (en) * | 2016-12-16 | 2021-07-13 | 包头稀土研究院 | Preparation method of rare earth aluminum calcium silicon iron composite alloy for steelmaking |
| CN113106197A (en) * | 2016-12-16 | 2021-07-13 | 包头稀土研究院 | Rare earth Al-Ca-Si-Fe composite alloy for steelmaking |
| CN107881369A (en) * | 2017-10-27 | 2018-04-06 | 大唐东北电力试验研究所有限公司 | Aluminium calcium antimony intermediate alloy inovulant and preparation method thereof |
| CN109778060A (en) * | 2019-03-26 | 2019-05-21 | 内蒙古锦和稀土功能材料有限公司 | Rare earth alloy and its preparation method and application |
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