CN102766801A - Rare earth Al-Ca-Fe alloy for rare earth micro-treated steel and preparation method thereof - Google Patents
Rare earth Al-Ca-Fe alloy for rare earth micro-treated steel and preparation method thereof Download PDFInfo
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- CN102766801A CN102766801A CN2012102910248A CN201210291024A CN102766801A CN 102766801 A CN102766801 A CN 102766801A CN 2012102910248 A CN2012102910248 A CN 2012102910248A CN 201210291024 A CN201210291024 A CN 201210291024A CN 102766801 A CN102766801 A CN 102766801A
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Abstract
The invention relates to a rare earth Al-Ca-Fe alloy for rare earth micro-treated steel and a preparation method thereof, and belongs to the technical field of ferroalloys. The rare earth Al-Ca-Fe alloy comprises, by weight, 28-65% of aluminum, 0.5-5% of calcium, 0.1-0.99% of rare earth, less than0.05% of impurity element carbon, less than0.4% of silicon, 0.02% of sulfur, less than0.02% of phosphor, less than1% of inevitable impurities and the balance ferrum. According to the preparation method, the finished alloy which meets requirements is prepared by utilizing pure aluminum ingots, rare earth, calcium metal and low-carbon high-quality scrap steel through a three-step method smelting process of an induction furnace. The rare earth Al-Ca-Fe alloy and the preparation method have the advantages that consumption of rare earth is reduced and the cost is reduced.
Description
Technical field
The invention belongs to the iron alloy technical field, refer more particularly to the little processing steel of a kind of rare earth with rare-earth aluminum-calcium-iron alloy and preparation method thereof.
Background technology
High-grade steel plate (as: car panel, household electrical appliances panel with steel etc.) all deep drawability, plasticity and the welding property to steel has proposed more and more stricter requirement.Research shows: the cleanliness factor that molten steel is high is to guarantee that steel have the important foundation of good use properties, contains the critical material performance index such as deep drawing quality that trace element (as: rare earth etc.) helps improving steel in the steel simultaneously.So how in smelting process, to improve cleanliness factor efficiently, making trace elements such as containing rare earth in the steel again simultaneously is the research topic that the metallargist pays close attention to.
Above-mentioned mentioned this type steel is generally carbon aluminium-killed steel.In order in smelting process, to obtain very low carbon content; Often need in molten steel, maintain very high oxygen concn; This has just caused still having higher residual oxygen in the molten steel after the decarburization, if these residual oxygen can not get effective removal, the use properties of steel is had very big hazardness.For this reason, add a large amount of aluminium molten steel is carried out deoxidation, but because the aluminum oxide deoxidation products that a large amount of adding generated of aluminium brings very big harm to casting direct motion, steel product quality equally.In order to eliminate the harm of aluminate, the way of mainly taking at present has: (1) prolongs the refining churning time, promotes inclusion floating.But this method will inevitably prolong refining time, increases production cost and reduces output.(2) change the liquid steel refining slag system and adsorb the aluminate that from molten steel, floats to the molten steel surface.It is long that this method exists refining time equally, and slag composition is difficult to the precisely controlled deficiency that waits.In addition, now extensively used technology is in molten steel, to add calcium constituent, make with steel in aluminate combine and form the calcium aluminium composite oxide, especially formation is like 12CaO7Al
2O
3This lower 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.
Because calcium metal is gasification easily under the steel-making temperature, therefore be not easy to add, yield is very low.The research worker has proposed the way that calcium constituent is processed with block calcium containing alloy is added in molten steel smelting or refining process.Document 1 (Guo Qingcheng: the Al-Ca-Fe alloy and the working method thereof that are used for final deoxygenation of molten steel; Publication number CN1439728A); (Guo Qingcheng etc.: a kind of high calcium that is used for deoxidation in steel making does not have Silcaz and preparation method thereof to reach document 2; Publication number CN101086029A) having proposed calcium ferroaluminium and document 3 (Xie Yingkai: composite deoxidizing agent aluminum-calcium-iron alloy for smelting steel, publication number CN101086028A) has proposed on the basis of kalzium metal, can add elements such as manganese, silicon and titanium and has all belonged to this type technology.
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.Document 4 (Hiroshi Hirata etc.: Steel Having Finely Dispersed Inclusions, US Patent 2006/0157162A1) record: after containing a certain amount of rare earth RE element in the molten steel, can form REAlO
3The inclusion of this lower melting point, soft is mentioned simultaneously, when rare earth can be avoided Al with calcium etc. further combination of element
2O
3The group bunch formation, produce high Clean Steel (as: bearing steel).The technology of its interpolation is: at first carry out aluminium deoxidation, add rare earth then and carry out inclusion removal and sex change.Document 5 (canal sky Sheng etc.: rare earth aluminum iron alloy; Publication number CN101078074A) invented a kind of new rare earth aluminum iron alloy, this alloy is easy to use, deoxidation and remove the high and small portion of residual rare earth of inclusion efficient and can give play to beneficial effect at the aspect of performance that improves steel.But in alloy, do not add useful calcium constituent, make it that effect aspect aluminate sex change and the removal is affected.
Along with going deep into of research, many research workers have proposed multielements such as employing rare earth, calcium and ferro-aluminum compound new method mutually.Document 6 (Xie Yingkai: be used to make steel rare earth aluminum based composite alloy, publication number CN101092657A) has proposed a kind of rare earth aluminum based composite alloy, content of rare earth 1～10%, and can add 1～5% elements such as calcium.Document 7 (canal sky Sheng etc.: a kind of rare-earth aluminum-calcium-iron alloy, publication number CN101519747A) has also proposed a kind of rare-earth aluminum-calcium alloy, in its composition; Content of rare earth 1～20%; Calcium contents 1～10%, document 8 (Chen Xiangming etc.: rare-earth aluminum-manganese Ca-Fe alloy and working method thereof, publication number CN102181606A); Content of rare earth 1～10%, calcium contents 1～3%.The compound refining efficiency of alloy in molten steel that improved of multielements such as these aluminium, calcium, rare earth.
But along with the more and more attention to rare earth resources protection, the price of rare earth is more and more expensive, and it is important how to reach the material property ten minutes that good metallurgical effect becomes reconciled with minimum rare earth addition.The inventor herein discovers: to above-mentioned related ferrous materials, contain (0.01～5) ppm in the steel, just (0.01～5) * 10
-4The rare earth of wt% trace just can make that steel performance is effectively improved.Otherwise too much rare earth addition can generate too much re inclusion, influences production direct motion and steel product quality, the rare earth resources that consumes simultaneously, and cost of alloy also obviously improves.
Summary of the invention
The object of the present invention is to provide the little processing steel of a kind of rare earth with rare-earth aluminum-calcium-iron alloy and preparation method thereof, reduced the consumption of rare earth resources, reduced cost.
The little processing steel of rare earth of the present invention uses the rare-earth aluminum-calcium-iron alloy composition to be: 28～65wt% aluminium, and 0.5～5wt% calcium, 0.1～0.99wt% rare earth, impurity element carbon are less than 0.05wt%, and silicon is less than 0.4%, and sulphur is less than 0.02%, and phosphorus is less than 0.02%.Other unavoidable impurities element total amount is less than 1%, and surplus is an iron.
Described rare earth is wherein single constituent element or the dual element combination that contains cerium, lanthanum element, and also comprising with lanthanum, Ce elements is other mishmetal of master, but the total content of lanthanum and cerium should account for more than 90% of total rare earth content.
The preparation method of rare-earth aluminum-calcium-iron alloy of the present invention: utilize fine aluminium ingot, rare earth, calcium metal and low-carbon (LC) high-quality steel scrap to prepare satisfactory finished product alloy through induction furnace three-step approach melting technology.Concrete process step is following:
(1) the first step: with fine aluminium ingot, rare earth is fusing of prepared using vacuum induction furnace and the rare earth aluminium initial alloy that is mixed with out certain ingredients; Smelting temperature is controlled at 950～1050 ℃; All melt back uniform mixing 4～10min; Under air, be cast into blocky rare earth aluminium initial alloy then, its size is (30～60) mm * (30～60) mm * (20～40) mm.This rare earth aluminium initial alloy composition is: aluminium 60～80%, rare earth 25～45%.
(2) second steps: aluminium ingot is being had the induction furnace fusing of argon shield atmosphere, and fusing finishes, and adds calcium alloy, and smelting temperature is controlled at 950～1050 ℃, and uniform mixing 4～10min is cast into aluminium calcium master alloy then.This aluminium calcium master alloy composition is: aluminium 60～80%, calcium 25～45%.Size is (30～60) mm * (30～60) mm * (20～40) mm.
(3) the 3rd steps: select high-quality steel scrap (Fe content >=98.5% for use; Other is an impurity element); And melt in conventional induction furnace with aluminium ingot, fusing is added on the rare earth aluminium initial alloy and the aluminium calcium master alloy that have prepared respectively in above-mentioned steps (1) and the step (2) after finishing again; Composition uniform mixing 4～10min, the alloy tapping temperature is controlled at 1050～1150 ℃.Be cast into the alloy block of (30～60) mm * (30～60) mm * (20～40) mm, naturally cooling is processed the alloy finished product in the air.
Alloy of the present invention has not only kept the meliority of forefathers at rare earth, aluminium, calcium multielement complex deoxidization; Its key is significantly to have reduced content of rare earth; Make cost of alloy obviously descend; Through with the strict optimum combination of calcium, aluminium content, can obtain the ideal refining efficiency, can make (0.01～5) * 10 residual in the molten steel simultaneously
-4The content of rare earth of wt% improves the quality in kind of steel.
Embodiment
Embodiment 1
(1) weighing aluminium block 15Kg, rare earth metal 5Kg melts 45min in vacuum induction furnace, and after fusing finished, tapping casting became rare earth aluminium initial alloy behind the uniform mixing 6min.Whole smelting process temperature is controlled at 970 ℃.This initial alloy composition is: aluminium 79.3%, and rare earth 20.3%, surplus is the impurity that smelting process is brought.
(2) weighing aluminium block 15Kg melts 45min in having the induction furnace of protective atmosphere, fusing is progressively added calcium metal 5Kg after finishing, and tapping casting becomes aluminium calcium master alloy behind the uniform mixing 5min.Whole smelting process temperature is controlled at 1020 ℃.This master alloy composition is: aluminium 77.1%, and calcium 22.5%, surplus is the impurity that smelting process is brought.
(3) select high-quality iron 48Kg for use, in having the intermediate frequency furnace of protective atmosphere, melt, progressively add aluminium ingot 35Kg after among the 40min, rare earth aluminium initial alloy 7Kg and the aluminium calcium master alloy 10Kg that the first step has prepared added in fusing evenly back.Composition uniform mixing 7min, the alloy tapping temperature is controlled at 1080 ℃.Be cast into the specific standard size, naturally cooling is processed the alloy finished product.
The prepared product composition that goes out is: Al:45.2wt%, and RE 0.9wt%, Ca 1.9wt%, surplus is an iron, the impurity element total content is less than 1%.Reached target component.
Embodiment 2:
(1) weighing aluminium block 60Kg, rare earth metal 20Kg melts 45min in vacuum induction furnace, and after fusing finished, tapping casting became rare earth aluminium initial alloy behind the uniform mixing 5min.Whole smelting process temperature is controlled at 940 ℃.This initial alloy composition is: aluminium 78.1%, and rare earth 21.3%, surplus is the impurity that smelting process is brought.
(2) weighing aluminium block 60Kg melts 45min in having the induction furnace of protective atmosphere, fusing is progressively added calcium metal 20Kg after finishing, and tapping casting becomes aluminium calcium master alloy behind the uniform mixing 5min.Whole smelting process temperature is controlled at 980 ℃.This master alloy composition is: aluminium 76.4%, and calcium 22.8%, surplus is the impurity that smelting process is brought.
(3) select high-quality iron 192Kg for use, in having the intermediate frequency furnace of protective atmosphere, melt, progressively add aluminium ingot 140Kg after among the 40min, rare earth aluminium initial alloy 28Kg and the aluminium calcium master alloy 40Kg that the first step has prepared added in fusing evenly back.Composition uniform mixing 6min, the alloy tapping temperature is controlled at 1100 ℃.Be cast into the specific standard size, naturally cooling is processed the alloy finished product.
The prepared product composition that goes out is: Al:46.1wt%, and RE 0.89wt%, Ca2.0wt%, surplus is an iron, the impurity element total content is less than 1%.Reached target component.
Claims (5)
1. the little processing steel of rare earth is used rare-earth aluminum-calcium-iron alloy, it is characterized in that composition is: 28～65wt% aluminium, and 0.5～5wt% calcium, 0.1～0.99wt% rare earth, impurity element carbon are less than 0.05wt%, and silicon is less than 0.4%, and sulphur is less than 0.02%, and phosphorus is less than 0.02%.Other unavoidable impurities element total amount is less than 1%, and surplus is an iron.
2. the little processing steel of rare earth according to claim 1 is used rare-earth aluminum-calcium-iron alloy, it is characterized in that, described rare earth is wherein single constituent element or the dual element combination that contains cerium, lanthanum element.
3. the little processing steel of rare earth according to claim 1 is used rare-earth aluminum-calcium-iron alloy, it is characterized in that, it is master's mishmetal that described rare earth comprises with lanthanum, Ce elements, and wherein, the total content of lanthanum and cerium should account for more than 90% of total rare earth content.
4. the preparation method of the described rare-earth aluminum-calcium-iron alloy of claim 1 is characterized in that, process step is following:
(1) be fusing of prepared using vacuum induction furnace and the rare earth aluminium initial alloy that is mixed with out certain ingredients with fine aluminium ingot, rare earth; Smelting temperature is controlled at 950～1050 ℃; All melt back uniform mixing 4～10min; Under air, be cast into blocky rare earth aluminium initial alloy then, this rare earth aluminium initial alloy composition is: aluminium 60～80%, rare earth 25～45%.
(2) aluminium ingot is being had the induction furnace fusing of argon shield atmosphere, fusing finishes, and adds calcium alloy, and smelting temperature is controlled at 950～1050 ℃, and uniform mixing 4～10min is cast into aluminium calcium master alloy then; This aluminium calcium master alloy composition is: aluminium 60～80%, calcium 25～45%;
(3) select the high-quality steel scrap for use; And in conventional induction furnace, melt with aluminium ingot; After fusing finishes; Be added on the rare earth aluminium initial alloy and the aluminium calcium master alloy that have prepared respectively in above-mentioned steps (1) and the step (2) again, composition uniform mixing 4～10min, the alloy tapping temperature has been controlled at 1050～1150 ℃; Be cast into alloy block, naturally cooling is processed the alloy finished product in the air.
5. method according to claim 4 is characterized in that described high-quality steel scrap is meant the steel scrap of Fe content >=98.5%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820698A (en) * | 2014-03-11 | 2014-05-28 | 包头稀土研究院 | Rare earth iron intermediate alloy and application 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 |
| CN111118251A (en) * | 2020-01-09 | 2020-05-08 | 河北尚权金属制品有限公司 | Aluminum-iron-calcium alloy for molten steel deoxidation and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519747A (en) * | 2009-03-11 | 2009-09-02 | 爱德洛（北京）科技有限公司 | Rare-earth aluminum-calcium-iron alloy |
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- 2012-08-16 CN CN2012102910248A patent/CN102766801A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519747A (en) * | 2009-03-11 | 2009-09-02 | 爱德洛（北京）科技有限公司 | Rare-earth aluminum-calcium-iron alloy |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820698A (en) * | 2014-03-11 | 2014-05-28 | 包头稀土研究院 | Rare earth iron intermediate alloy and application 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 |
| CN111118251A (en) * | 2020-01-09 | 2020-05-08 | 河北尚权金属制品有限公司 | Aluminum-iron-calcium alloy for molten steel deoxidation and preparation method thereof |
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Application publication date: 20121107 |