CN101994054A - Intermediate containing ultrafine oxide ferroalloy and preparation method thereof - Google Patents
Intermediate containing ultrafine oxide ferroalloy and preparation method thereof Download PDFInfo
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- CN101994054A CN101994054A CN2009100131276A CN200910013127A CN101994054A CN 101994054 A CN101994054 A CN 101994054A CN 2009100131276 A CN2009100131276 A CN 2009100131276A CN 200910013127 A CN200910013127 A CN 200910013127A CN 101994054 A CN101994054 A CN 101994054A
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Abstract
The invention discloses an intermediate containing an ultrafine oxide ferroalloy. The intermediate containing the ultrafine oxide ferroalloy is a ferroalloy containing 3.0*106-8.0*106/mm<3> titanium oxide with the grain diameters of 0.2-2 mum and the balance of Fe and inevitable impurities. The preparation method comprises the following steps of: adjusting the temperature of molten iron to be 150 DEG C higher than the line temperature of a liquid-phase; adjusting the oxygen content of molten steel to be 1000-1500 ppm; adding ferrotitanium to the molten steel, wherein the addition amount is 0.5-0.9 percent by weight of the molten iron; adding a magnesium aluminum alloy, wherein the addition amout of the magnesium aluminum alloy is 0.3-0.5 percent of the molten iron; and casting the intermediate into a block or ball shape after being melted and discharged from the furnace. The invention has simple process and low cost, avoids the agglomeration problem, improves the wettability between metal and nonmetal and ensures the stable yield of oxide particles in steel.
Description
Technical field
The invention belongs to and belong to metallurgical technology field, relate to a kind of metallurgical material, particularly a kind of superfine oxide iron alloy intermediate and preparation method thereof that contains.
Background technology
In recent years, the metallargist has realized that some fine foreign matter can significantly improve some performance of steel in the solid state transformation process of steel.Typical example is the oxide compound metallurgical technology, and this technology is initiated and is applied in the Iron and Steel Production for the researchist of Japan.Its basic principle is the titan oxide particles that forms small and dispersed in steel, because the titanium oxide free energy is very low, and at high temperature also can stable existence.Under the welding technique condition of superpower, large-line energy, welding temperature is higher, thereby the austenite grain boundary that the titanium oxide ultrafine particle can the pinning welded heat affecting zone, and the tissue after the refinement welding improves the steel toughness of welded heat affecting zone.This technology at first is applied on some the high strength structure steel of Japan such as kinds such as pipe line steel, large-line energy welding steel.This good action of ultrafine particle in steel mainly depends on its tiny degree and disperse distributed degrees, and particle is more little, the disperse degree is high more, and be just strong more to the refining effect of structure of steel.
In order to obtain the oxide particle of small and dispersed, two kinds of methods of main at present employing, a kind of method is at the extremely low aluminium content of refining process control, adopt weak deoxidization technique, to keep molten steel after refining still to contain certain free oxygen level (20～30ppm), these free oxygen will be separated out in process of setting, and generate stable oxide with steel interalloy element titanium reaction, see " the clean quiet steel process of setting oxide compound of titaniferous low-carbon (LC) separate out and grow up " (Second InternationalConference on Advanced Structural Steels, 1160～1169).Because molten steel solidification time of clock in a measure only from the liquidus line to the solidus curve, therefore formed oxide particle is minimum, these tiny oxide particles effectively the refinement steel solidified structure, suppressed growing up of crystal grain.But this method needs the content of aluminium in the molten steel must be less than 0.001%.Owing in deoxygenated alloy, refractory materials and slag former, all contain aluminium element, these aluminium are under the effect of physical and chemical condition in the steelmaking process, must shift to molten steel, therefore in actual production, if it is quite difficult that aluminium is controlled at below 0.001%, therefore also is difficult for realization industry and produces greatly.On the other hand, the free oxygen after the refining in the molten steel is difficult to control, and free oxygen level is low can't to form a large amount of oxide particles, does not have the thinning solidification structure effect.Otherwise free oxygen level height will cause a large amount of subsurface bubbles of strand, has a strong impact on slab quality.Another kind method be earlier with titanium oxide fine powder and iron powder at a certain temperature sintering become a useful person, make the master alloy body that oxycompound is mingled with, then this master alloy is joined in the molten steel, the iron-based body melts the rear oxidation titanium and can be distributed in the molten steel.See and " contain nano-TiO
2Oxide compound iron alloy intermediate and its production and use " (application number: CN200610030722.7, publication number: CN101135023).Owing to no longer need to carry out complicated inclusion morphology control, smelting procedure is thought of a way in and is simplified relatively.But powder is in mixing process, and the ultrafine titanium oxide particle is difficult to be evenly distributed in the iron-based body, and particle agglomeration is inevitable, and in addition, the oxide particle in the sintering process is excessively grown up and can't be solved.
As mentioned above, the production method with fine oxide dispersion steel is applied to also have many open questions in the mass-produced iron and steel technology.
Summary of the invention
Basic thought of the present invention is to make superfine oxide to be dispersed in as far as possible uniformly in the steel, to avoid inclusion steel product quality is brought disadvantageous effect.Because the more little disperse degree of particle is high more in the steel, its refining effect to structure of steel is just strong more; Otherwise particle is big more in the steel, the disperse degree is poor more, has just become deleterious inclusion.Therefore, wish the tiny as far as possible and disperse distribution of oxide inclusion.
The object of the present invention is to provide a kind of superfine oxide iron alloy intermediate and preparation method thereof that contains, guaranteeing superfine oxide particle stable receipts in steel, and keep the disperse to distribute.Grain growths such as the phase transformation in the process of metal working thereafter, thermal treatment and welding are played effective restraining effect.
At above-mentioned purpose, main technical schemes of the present invention is:
Raw material comprise technically pure iron or soft steel, liquid level protection slag charge, ferrotianium, magnalium and oxygenation agent (for the raw material of band oil or corrosion, carry out oil removing, rust cleaning pre-treatment earlier, and oven dry by with).It is that 0.2 μ m～2 μ m titanium-containing oxide quantity are 3.0 * 10 that the intermediate of preparation contains particle diameter
6～8.0 * 10
6Individual/mm
3, all the other are Fe and some unavoidable impurities.
Liquid level protection slag charge is with NaF
250%～60%, the weight percentage proportioning of BaCl 25%～35%, all the other are CaF
2, even through mechanically mixing, standby.
Concrete preparation process may further comprise the steps:
(1) technically pure iron or high-quality soft steel are gone into stove, the energising heat fused, it is overheated to continue then, and liquid steel temperature is higher than liquidus temperature more than 150 ℃.
(2) by a certain percentage the oxygenation agent is joined in the steel, add-on is according to the difference of oxygenation agent type and difference, and the molten steel oxygen level is adjusted to 1000～1500ppm the most at last.
(3) add the liquid level covering slag to fusing, make liquid level that the sealing of one deck slag be arranged, add-on is 3%～5% of a steel quality.
(4) in molten steel, add ferrotianium by a certain percentage, the even composition of hand mixing, add-on is 0.5%～0.9% of a molten steel weight.
(5) add an amount of magnalium, slough residual oxygen in the molten steel, add-on is 0.3%～0.5% of a molten steel weight.
(6) melting finish come out of the stove after, intermediate is cast into block or spherical.
Related liquid steel temperature is higher than liquidus temperature more than 150 ℃ in this technical scheme, is in order to improve the solubleness of oxygen and oxide compound in the molten steel, but examines filter fire resisting material of furnace body ability to bear, generally is no more than 1720 ℃;
The oxygenation agent that relates in this technical scheme can use (a) to be called FeO, Fe
2O
3, MnO and MnO
2Oxide compound; (b) also can for the gas of oxidation molten steel (as O
2) and with the gas of above-mentioned gas with inert gas dilutions such as Ar.And the oxygen activity in the molten steel is increased to 1000～1500ppm, guarantee to also have in the molten steel enough oxygen and titanium reaction to generate titanium oxide.
In order to reduce cost, titanium content is 30% weight percentage in the ferrotianium that relates in this technical scheme, if do not consider that the cost problem also can adopt the ferrotianium of other titanium content as reductor.
In the related molten steel oxygen activity adjustment process,, oxygen activity can influence the quantity that generates oxide compound in this technical scheme if being lower than 1000ppm; If oxygen activity is higher than 1500ppm, then easily reduce the recovery rate of iron and steel stock.
In this technical scheme in the related magnalium Mg content by weight percentage composition be 10%, Mg content is too high to cause that easily spray is quick-fried, Mg content is crossed the low deoxidation effect that has weakened alloy on the one hand, is unfavorable for generating ultra-fine magnesium titanium complex inclusion on the other hand.If it is quick-fried effectively to control spray, also can adopt Mg content greater than 10% magnalium.
(1) technology is simple, cost is low;
(2) adopt the present invention to avoid directly adding oxide powder to molten steel, its recovery rate is very low and the problem of " reunion " takes place easily, improved metal and nonmetal between wettability and also guaranteed the stable recovery rate of oxide particle in steel.
(3) iron alloy density of the present invention is big, and near the density of steel, so oxide compound is easy to add the recovery rate height.After adding 0.1% the intermediate be not more than molten steel weight in the molten steel, the titanium-containing oxide of 0.2 μ m～2 μ m can reach 60～80/mm in the solidified structure
2
Embodiment
Add Fe with molten steel below
2O
3The oxygenation agent is an example, adopts the high temperature resistance furnace melting, and intermediate manufacture craft process and product feature are described.
Embodiment 1:
Adopt the high temperature resistance furnace melting, the 500g technically pure iron is added in the stove, the energising heat fused, it is overheated to continue then, and liquid steel temperature is risen to 1680 ℃.With Fe
2O
3Powder 10g joins in the molten steel, stirs slightly, after 30 seconds, adopts apparatus for determination of oxygen to decide oxygen, and the actual measurement oxygen activity is 1200ppm; Adding composition then is NaF
260%, CaF
210%, the liquid level protection slag charge 15g of the weight percentage proportioning of BaCl 30% makes liquid level that the sealing of one deck slag be arranged; Add titanium content then and be 30% ferrotianium 3.75g, after stirring, add the magnalium 2g that contains magnesium 10% (weight percentage), slough residual oxygen; Melting finish come out of the stove after, alloy is cast into block or spherical.
Form, the distribution of inclusion observed in the sampling back on intermediate.The oxide content of 0.2 μ m～2 μ m is 4 * 10 in the intermediate
6Individual/mm
3, the inclusion globulate, through energy spectrum analysis, these inclusiones mainly contain Ti and O element, also contain a spot of Mg and Al element simultaneously.
Embodiment 2:
Adopt the high temperature resistance furnace melting, the 1000g technically pure iron is added in the stove, the energising heat fused, it is overheated to continue then, and liquid steel temperature is risen to 1700 ℃.With Fe
2O
3Powder 22g joins in the molten steel, stirs slightly, after 30 seconds, adopts apparatus for determination of oxygen to decide oxygen, and the actual measurement oxygen activity is 1500ppm; Adding composition then is NaF
260%, CaF
210%, the liquid level protection slag charge of the weight percentage proportioning of BaCl 30% makes liquid level that the sealing of one deck slag be arranged; Add titanium content then and be 30% ferrotianium 8g, after stirring, add the magnalium 4g that contains magnesium 10% (weight percentage), slough residual oxygen; Melting finish come out of the stove after, alloy is cast into block or spherical.
Form, the distribution of inclusion observed in the sampling back on intermediate.The oxide content of 0.2 μ m～2 μ m is 6 * 10 in the intermediate
6Individual/mm
3, the inclusion globulate, through energy spectrum analysis, these inclusiones mainly contain Ti and O element, also contain a spot of Mg and Al element simultaneously.
Other embodiment sees the following form, and technological process is identical with embodiment 1,2, and different is the addition of molten steel temperature and oxygenation agent type and various raw materials.
Claims (4)
1. one kind contains superfine oxide iron alloy intermediate, it is characterized in that, described superfine oxide iron alloy intermediate is that to contain titanium oxide, the quantity that particle diameter is 0.2 μ m～2 μ m be 3.0 * 10
6～8.0 * 10
6Individual/mm
3, surplus is the iron alloy of Fe and inevitable impurity.
2. a kind of superfine oxide iron alloy intermediate that contains according to claim 1 is characterized in that the raw material sources of above-mentioned intermediate are in technically pure iron or soft steel, ferrotianium, magnalium and oxygenation agent.
3. a kind of superfine oxide iron alloy intermediate that contains according to claim 2 is characterized in that described oxygenation agent is FeO, Fe
2O
3, MnO and MnO
2In oxide compound or the O2 oxygenation gas one or more.
4. produce a kind of its preparation method that contains superfine oxide iron alloy intermediate as claimed in claim 1 for one kind, it is characterized in that,
Concrete preparation process may further comprise the steps:
(1) technically pure iron or soft steel are gone into stove, the energising heat fused, it is overheated to continue then, and liquid steel temperature is higher than liquidus temperature more than 150 ℃;
(2) the oxygenation agent is joined in the steel, the molten steel oxygen level is adjusted to 1000～1500ppm the most at last;
(3) add the liquid level covering slag to fusing, make liquid level that the sealing of one deck slag be arranged, add-on is 3～5% of a steel quality, and its liquid level protects slag charge to be, by weight percentage, and NaF
250%～60%, BaCl 25～35%, and all the other are CaF
2
(4) by in molten steel, adding ferrotianium, the even composition of hand mixing, add-on is 0.5%～0.9% of a molten steel weight;
(5) add magnalium, slough residual oxygen in the molten steel, add-on is 0.3%～0.5% of a molten steel weight;
(6) melting finish come out of the stove after, intermediate is cast into block or spherical.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333991A (en) * | 2013-07-03 | 2013-10-02 | 东北大学 | Ferritic alloy for adjusting content of dissolved oxygen in molten steel, and preparation and usage method thereof |
| CN111690834A (en) * | 2020-04-22 | 2020-09-22 | 南京国重新金属材料研究院有限公司 | Preparation method of nickel-based high-temperature alloy with gradient oxygen content |
| CN111763793A (en) * | 2020-05-27 | 2020-10-13 | 山西太钢不锈钢股份有限公司 | Smelting method for manufacturing stainless steel with high oxygen content |
| CN112226668A (en) * | 2020-10-13 | 2021-01-15 | 五矿营口中板有限责任公司 | Method for manufacturing low-alloy steel plate containing aluminum and suitable for large-line weldable |
| CN113072384A (en) * | 2021-03-29 | 2021-07-06 | 安徽工业大学 | Novel oxide metallurgy process |
Citations (1)
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| CN101135023A (en) * | 2006-08-31 | 2008-03-05 | 宝山钢铁股份有限公司 | Nano TiO2 oxide containing ferroalloy intermediate and preparation method and uses thereof |
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| CN101135023A (en) * | 2006-08-31 | 2008-03-05 | 宝山钢铁股份有限公司 | Nano TiO2 oxide containing ferroalloy intermediate and preparation method and uses thereof |
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| 尚德礼等: "凝固过程中质点强化钢铁材料的研究进展", 《鞍钢技术》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333991A (en) * | 2013-07-03 | 2013-10-02 | 东北大学 | Ferritic alloy for adjusting content of dissolved oxygen in molten steel, and preparation and usage method thereof |
| CN103333991B (en) * | 2013-07-03 | 2015-02-25 | 东北大学 | Ferritic alloy for adjusting content of dissolved oxygen in molten steel, and preparation and usage method thereof |
| CN111690834A (en) * | 2020-04-22 | 2020-09-22 | 南京国重新金属材料研究院有限公司 | Preparation method of nickel-based high-temperature alloy with gradient oxygen content |
| CN111763793A (en) * | 2020-05-27 | 2020-10-13 | 山西太钢不锈钢股份有限公司 | Smelting method for manufacturing stainless steel with high oxygen content |
| CN112226668A (en) * | 2020-10-13 | 2021-01-15 | 五矿营口中板有限责任公司 | Method for manufacturing low-alloy steel plate containing aluminum and suitable for large-line weldable |
| CN112226668B (en) * | 2020-10-13 | 2021-06-22 | 五矿营口中板有限责任公司 | Method for manufacturing low-alloy steel plate containing aluminum and suitable for large-line weldable |
| CN113072384A (en) * | 2021-03-29 | 2021-07-06 | 安徽工业大学 | Novel oxide metallurgy process |
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