CN102828000A - Metallurgical V-N microalloying and compound deoxidation cored wire - Google Patents
Metallurgical V-N microalloying and compound deoxidation cored wire Download PDFInfo
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Abstract
A metallurgical V-N microalloying and compound deoxidation cored wire contains a core wire and a cladding steel belt. The technical key point of the cored wire is as follows: the core wire of the cored wire consists of a vanadium-increasing agent, a nitrogen-increasing agent and a deoxidizing nitrogen-fixing agent of which particle sizes are less than 6mm, wherein the vanadium-increasing agent is ferrovanadium, nitrided ferrovanadium or vanadium pentoxide; the nitrogen-increasing agent is ferrosilicon nitride, silicomanganese nitride, ferromanganese nitride, ferrochromium nitride, silicon nitride, aluminum nitride or calcium cyanamide; and the deoxidizing nitrogen-fixing agent contains one or more of aluminum, calcium, magnesium and barium, and can also contain one or more of titanium, zirconium, niobium, manganese, chromium, silicon, carbon and iron. By adopting the cored wire, the V/N ratio of steel can get closer to the optimal proportion, the enhancing function of vanadium can be utilized furthest, vanadium resources can be saved, the recovery rate of nitrogen is high, the nitrogen content is stable, the compound deoxidation function can also be realized, the V-N microalloying cost can be reduced and the quality of steel can be increased.
Description
Technical field
The present invention relates to technical field of ferrous metallurgy, specifically a kind of metallurgy is with the cored-wire of v n micro alloying and complex deoxidization.
Background technology
The microalloying of vanadium and nitrogen is the main method of producing HSLA (for example other Deformed Steel Bars of HRB400 higher level).In containing vanadium steel, add the nitrogen element, can in steel, form the carbide or the nitride of vanadium, the dual function through its deposition precipitation strength and crystal grain thinning can improve the ys of steel greatly, and make steel have good plasticity, toughness and weldableness concurrently.
When steel was carried out the microalloying of vanadium and nitrogen, the content of vanadium in the steel and the ratio of nitrogen content (being called for short vanadium nitrogen than V/N) had very big influence to the performance of steel.Under the situation that content of vanadium is constant in steel, along with the raising (corresponding V/N ratio reduces) of nitrogen content, the ys of steel obviously improves.When V/N ratio reaches desirable stoicheiometry 3.64 (being equivalent to atomic ratio 1:1), vanadium can farthest be separated out, thereby reaches best strengthening effect.If V/N ratio surpasses 3.64, then have the part vanadium still solid solution in steel, fail to play the effect that deposition is separated out.Therefore if can improve the content of nitrogen in steel, make that V/N ratio drops to below 3.64 in the steel, usually improve the utilization ratio of vanadium with regard to the nitrogen unit of cheapness capable of using; When improving steel strength; Reduce the content of vanadium in the steel, thereby reach the vanadium resource of conserve expensive, reduce the purpose of steel-making cost.
At present, the method for molten steel being carried out the microalloying of vanadium and nitrogen mainly contains three kinds: the one, add VN alloy (claiming vanadium nitride again), and the 2nd, add ferrovanadium nitride, the 3rd, when adding vanadium iron, add the ferro-silicon nitride alloy.But these three kinds of methods all exist certain defective.
(1) VN alloy: the nitride that is the vanadium that makes through the method for vacuum carbon reduction and nitrogenize with Vanadium Pentoxide in FLAKES.The content of vanadium of VN alloy is than higher, and generally 76% to 80%, and nitrogen content is generally between 12% to 16%, so V/N ratio is between 6.5 to 5.Its shortcoming one is that V/N ratio is too high; The 2nd, VN alloy density is less; After adding block VN alloy in the molten steel, can swim in molten steel above, cause part VN alloy scaling loss; The recovery of vanadium and nitrogen is all lower; Particularly the recovery of nitrogen only 40% to 50%, and is more much lower than the recovery 80% of vanadium, further strengthened the V/N ratio in the steel.Therefore use VN alloy separately, the utilization ratio of vanadium is not high.Chinese patent CN1818086A has proposed a kind of the VN alloy powder to be processed the patent of cored-wire, though this method can improve the recovery of VN alloy, only contains VN alloy and a small amount of niobium titanium alloy in the cored-wire of this patent; Do not add rich nitrogen alloy, therefore, when using the described cored-wire of this patent that molten steel is carried out microalloying; If will increase the nitrogen content in the steel; Just must increase content of vanadium simultaneously, can not adjust that V/N ratio is to optimum proportion in the steel, the utilization ratio of vanadium is still lower.
(2) ferrovanadium nitride: be with the alloy of vanadium iron through making behind the nitriding treatment.Contain the iron about 40% in the ferrovanadium nitride, content of vanadium is 40% ~ 45%, and nitrogen content is 9% to 13%.Its V/N ratio is about 4.5, and relatively near best vanadium nitrogen ratio, and density is also high than VN alloy, and therefore, in theory, when the interpolation ferrovanadium nitride carried out microalloying to steel, the recovery of nitrogen should be higher than VN alloy.But, facts have proved that the recovery of nitrogen is lower than VN alloy on the contrary when adding ferrovanadium nitride.Reason is, contained nitrogen in the ferrovanadium nitride, and some nitrogen is not that solid solution is in alloy; But be adsorbed in the alloy with gaseous state, can become gas after this part nitrogen is heated and from molten steel, emerge, be difficult to be dissolved in the molten steel; Therefore the recovery of nitrogen is not high, and the nitrogen content fluctuation of adding in the ferrovanadium nitride is bigger, thereby the nitrogen content in the steel is unstable; Cause the ys of finished steel to occur being difficult to control steel product quality than great fluctuation process.
(3) add vanadium iron and ferro-silicon nitride: Chinese patent CN1405351A has proposed to add respectively the method that blocky rich nitrogen alloy and vanadium-containing alloy carry out the microalloying of vanadium and nitrogen, and its objective is by rich nitrogen alloy increases nitrogen content, reduction V/N ratio.The method of rich nitrogen alloy of the described interpolation of this patent and vanadium-containing alloy is in the process of tapping, to add in the molten steel with deoxygenated alloy.There are three problems in this addition means, and the one, because blocky rich nitrogen alloy density is lower, even be lower than the density of slag, can swim in above the slag after adding in the molten steel, cause the alloy part scaling loss; The 2nd, rich nitrogen alloy melting point is higher, poor thermal conductivity, and do not soak into molten steel, add in the molten steel after, the burn-off rate of bulk alloy in molten steel is very slow, only depends on the impact of molten steel in the tapping process to stir and is difficult to make rich nitrogen alloy to disperse to get in the molten steel; The 3rd, deoxidation of molten steel is not thorough during tapping, and oxygen level is higher, and the bulk alloy surface is prone to generate the film of oxide compound, has further reduced solubleness and the velocity of diffusion of nitrogen in molten steel; These three defectives cause the most of the nitrogen in the rich nitrogen alloy to become nitrogen bubble from molten steel, to emerge, be difficult to be dissolved in the molten steel, cause the recovery of nitrogen on the low side, and unstable, generally fluctuation between 20% to 50%.Therefore the usage quantity of rich nitrogen alloy is bigger, and the nitrogen pick-up cost is higher.Simultaneously, nitrogen in steel content is unstable, can cause the ys of finished steel to occur being difficult to control steel product quality than great fluctuation process.This point is particularly unfavorable to the production of anti-seismic steel bar.This is because anti-seismic steel bar has more strict requirement to the fluctuation range of steel ys.
Summary of the invention
The purpose of this invention is to provide the cored-wire of a kind of metallurgy with v n micro alloying and complex deoxidization.
The objective of the invention is to realize like this: it includes core and coated steel band, it is characterized in that: core is made up of following composition, its each component granularity less than 6mm and in the core gross weight shared weight percent be respectively:
Contain the iron alloy of vanadium or oxide compound conduct increasing vanadium agent, 50%～80% of VN alloy or vanadium;
Nitrogenous and the rich nitrogen alloy that do not contain vanadium is as nitrogen promoter, and 10% to 40%;
The deoxidation nitrogen fixation agent of forming by strong deoxidation metal, alloy or compound, 5% to 25%.
Each component granularity is preferably less than 2mm.
Increasing the vanadium agent is vanadium iron, ferrovanadium nitride or Vanadium Pentoxide in FLAKES.
Nitrogen promoter is ferro-silicon nitride, nitrogenize silicomanganese, nitrogenize ferromanganese, nitrided ferro-chromium, silicon nitride, aluminium nitride AlN or carbon CaCl2.
The deoxidation nitrogen fixation agent is at least a in metallic aluminium, calcium, magnesium, the barium or the alloy be made up of them.
Described deoxidation nitrogen fixation agent also can include in titanium, zirconium, niobium, manganese, chromium, silicon, carbon and the iron one or more except the alloy that contains at least a metallic aluminium, calcium, magnesium, barium or be made up of them.
Principle of the present invention
(1) effect of nitrogen promoter: the present invention is on the basis that increases the vanadium agent; Added the nitrogen promoter that does not contain vanadium; Make V/N in the cored-wire than reducing, and can adjust V/N ratio, can make the V/N ratio in the steel reach desired quantity through the proportioning that adjustment increases vanadium agent and nitrogen promoter.Interpolation does not contain the nitrogen promoter of vanadium separately, makes V/N than reducing, and is the key distinction of the present invention and Chinese patent CN1818086A;
(2) effect of deoxidation nitrogen fixation agent: oxygen level in the molten steel and nitrogen content exist the relation of competition, and oxygen height then nitrogen is low, and the low then nitrogen of oxygen is high.Simultaneously, the most fusing point of rich nitrogen alloy is high, and does not soak into molten steel, thereby the burn-off rate of blocky rich nitrogen alloy in molten steel is slower.The deoxidation nitrogen fixation agent that the present invention adopts belongs to strong reductor mainly by low melting point metal or alloy compositions such as aluminium, calcium, magnesium, barium for molten steel.The effect of deoxidation nitrogen fixation agent has three: one, and low melting point alloys such as aluminium, calcium, magnesium, barium can at high temperature form mutual melt with rich nitrogen alloy, can reduce the fusing point of rich nitrogen alloy, promote the decomposition of rich nitrogen alloy in molten steel, increase the wellability of rich nitrogen alloy and molten steel; The 2nd, the metal of aluminium, calcium, magnesium, barium and alloy belong to strong reductor; Their generation composite oxides that can react with the oxygen in the molten steel, and float to slag, play the effect of complex deoxidization; In further reduction molten steel, in the oxygen level, can increase the solubleness of nitrogen; The 3rd, alloying element aluminium, calcium, magnesium, barium and the titanium of composition deoxidation nitrogen fixation agent, zirconium, niobium, manganese, chromium etc. are the elements that reduces the activity quotient of nitrogen in molten steel, add these elements and can improve the solubleness of nitrogen in molten steel.
(3) effect of cored-wire: the solubleness of nitrogen in molten steel is lower; 1600 when spending only about 0.04%; When the nitrogen content in the molten steel surpassed its solubleness, nitrogen can become nitrogen bubble and from molten steel, emerge, and this is the low and unsettled major cause of the recovery that causes nitrogen.The present invention will increase vanadium agent, nitrogen promoter and deoxidation nitrogen fixation agent and be broken into powder; After mixing by proportioning, make in the cored-wire feeding molten steel, because the dissolving of nitrogen killer in molten steel such as vanadium, aluminium, manganese, calcium, magnesium; The area with high mercury that can occur nitrogen killer in the part of molten steel; Thereby the solubleness of nitrogen can improve greatly in this zone, that is to say, the fusing of vanadium iron and deoxidation nitrogen fixation agent can promote the dissolving of nitrogen in molten steel.But precondition is to increase in molten steel, to melt after vanadium agent, nitrogen promoter and deoxidation nitrogen fixation agent must mix with the epigranular less than 6mm.Make an addition to respectively in the molten steel with the bulk greater than 6mm if will contain the alloy of vanadium and nitrogen, because the big and rich nitrogen alloy density of vanadium iron density is little, then be not together in the melting range of the melting range of vanadium iron and nitrogen, and it is many that the effect of fixed nitrogen will differ from.The effect of cored-wire at first is in the alloy feeding molten steel with powdered form, under the effect of gas stirring, makes mixed powdered alloy can disperse to get into fusing fast in the molten steel; Next is to let powder fusing in the molten steel depths in the cored-wire, and under the ferrostatic pressure effect, the pressure that forms nitrogen bubble increases, and has been equivalent to improve the solubleness of nitrogen, thereby can have further improved the recovery of nitrogen.
The positively effect that adopts the present invention to produce
1. increase the proportioning of vanadium agent and nitrogen promoter through adjustment, can adjust the V/N ratio in the steel, make it, can farthest bring into play the strengthening effect of vanadium, realize practicing thrift vanadium resource, reduce the purpose of steel-making cost more near optimum proportion.
2. the recovery of nitrogen can be brought up to more than 80%, and the nitrogen promoter addition reduces, and can further reduce steel-making cost;
3. nitrogen in steel stable content, thereby make the stable performance of steel, be particularly suitable for the production of anti-seismic steel bar.
Cored-wire of the present invention has the effect of complex deoxidization concurrently, and alternative part deoxygenated alloy reduces steel-making cost.
Embodiment
Embodiment 1:50 vanadium iron, ferro-silicon nitride, silicocalcium are broken into granularity less than 6mm, account for 60% by vanadium iron, ferro-silicon nitride accounts for 20%, and silicocalcium accounts for 20% ratio batching and mixes, and is made into cored-wire then.In converter, smelt the 20SiMn steel, in the converter tapping process, molten steel is carried out preliminary dexidation and alloying; Then ladle is sent into ladle refining furnace or Argon station; With in the speed feeding ladle of above-mentioned cored-wire with 3 meter per seconds, add-on is pressed 1.2 kilograms of/ton molten steel calculating of powder weight in the cored-wire, in line feeding, in molten steel, is blown into argon gas and stirs with feeding wire machine; Line feeding finishes continued stirred 1 minute, sampling tapping then.Content of vanadium in the actual measurement molten steel is 0.034%, and nitrogen content is 0.0101%.
Embodiment 2:VN alloy, nitrogenize silicomanganese and metallic aluminium powder are broken into granularity less than 6mm, account for 75% by VN alloy, the nitrogenize silicomanganese accounts for 15%, and aluminium powder accounts for 10% ratio batching and mixes, and is made into cored-wire then.In converter, smelt the 20SiMn steel, in the converter tapping process, molten steel is carried out preliminary dexidation and alloying; Then ladle is sent into ladle refining furnace or Argon station; With in the speed feeding ladle of above-mentioned cored-wire with 3 meter per seconds, add-on is pressed 0.65 kilogram of/ton molten steel calculating of powder weight in the cored-wire, in line feeding, in molten steel, is blown into argon gas and stirs with feeding wire machine; Line feeding finishes continued stirred 1 minute, sampling tapping then.Content of vanadium in the actual measurement molten steel is 0.035%, and nitrogen content is 0.0109%.
Embodiment 3:50 vanadium iron, ferro-silicon nitride, silicocalcium and metallic aluminium powder are broken into granularity less than 2mm, account for 63% by vanadium iron, ferro-silicon nitride accounts for 22%, and metallic aluminium powder accounts for 10%, and silicocalcium accounts for 5% ratio batching and mixes, and is made into cored-wire then.In converter, smelt the 20SiMn steel, in the converter tapping process, molten steel is carried out preliminary dexidation and alloying; Then ladle is sent into ladle refining furnace or Argon station; With in the speed feeding ladle of above-mentioned cored-wire with 3 meter per seconds, add-on is pressed 1.1 kilograms of/ton molten steel calculating of powder weight in the cored-wire, in line feeding, in molten steel, is blown into argon gas and stirs with feeding wire machine; Line feeding finishes continued stirred 1 minute, sampling tapping then.Content of vanadium in the actual measurement molten steel is 0.033%, and nitrogen content is 0.0096%.
Embodiment 4:50 vanadium iron, ferro-silicon nitride and passivation carbide of calcium are broken into granularity less than 2mm, account for 67% by vanadium iron, ferro-silicon nitride accounts for 27%, and passivation carbide of calcium accounts for 6% ratio batching and mixes, and is made into cored-wire then.In converter, smelt the 20SiMn steel, in the converter tapping process, molten steel is carried out preliminary dexidation and alloying; Then ladle is sent into ladle refining furnace or Argon station; With in the speed feeding ladle of above-mentioned cored-wire with 3 meter per seconds, add-on is pressed 1.6 kilograms of/ton molten steel calculating of powder weight in the cored-wire, in line feeding, in molten steel, is blown into argon gas and stirs with feeding wire machine; Line feeding finishes continued stirred 1 minute, sampling tapping then.Content of vanadium in the actual measurement molten steel is 0.052%, and nitrogen content is 0.0151%.
Embodiment 5:VN alloy, nitrogenize silicomanganese and metallic aluminium powder and ferrotianium are broken into granularity less than 6mm, account for 70% by VN alloy, the nitrogenize silicomanganese accounts for 15%, and aluminium powder accounts for 10%, and ferrotianium accounts for 5% ratio batching and mixes, and is made into cored-wire then.In converter, smelt the 20SiMn steel, in the converter tapping process, molten steel is carried out preliminary dexidation and alloying; Then ladle is sent into ladle refining furnace or Argon station; With in the speed feeding ladle of above-mentioned cored-wire with 3 meter per seconds, add-on is pressed 0.65 kilogram of/ton molten steel calculating of powder weight in the cored-wire, in line feeding, in molten steel, is blown into argon gas and stirs with feeding wire machine; Line feeding finishes continued stirred 1 minute, sampling tapping then.Content of vanadium in the actual measurement molten steel is 0.034%, and nitrogen content is 0.0106%.
It is pointed out that top embodiment do not contain full content of the present invention.
Claims (6)
1. a metallurgy is with the cored-wire of v n micro alloying and complex deoxidization, and it includes core and coated steel band, it is characterized in that: core is made up of following composition, and its each component granularity is less than 6mm, and shared weight percent is respectively in the core gross weight:
Contain the iron alloy of vanadium or oxide compound conduct increasing vanadium agent, 50%～80% of VN alloy or vanadium;
Nitrogenous and the rich nitrogen alloy that do not contain vanadium is as nitrogen promoter, and 10% to 40%;
The deoxidation nitrogen fixation agent of forming by strong deoxidation metal, alloy or compound, 5% to 25%.
2. metallurgy according to claim 1 is characterized in that with the cored-wire of v n micro alloying and complex deoxidization: each component granularity is preferably less than 2mm.
3. metallurgy according to claim 1 is characterized in that with the cored-wire of v n micro alloying and complex deoxidization: increasing the vanadium agent is vanadium iron, ferrovanadium nitride or Vanadium Pentoxide in FLAKES.
4. metallurgy according to claim 1 is characterized in that with the cored-wire of v n micro alloying and complex deoxidization: nitrogen promoter is ferro-silicon nitride, nitrogenize silicomanganese, nitrogenize ferromanganese, nitrided ferro-chromium, silicon nitride, aluminium nitride AlN or carbon CaCl2.
5. metallurgy according to claim 1 is characterized in that with the cored-wire of v n micro alloying and complex deoxidization: the deoxidation nitrogen fixation agent is at least a in metallic aluminium, calcium, magnesium, the barium or the alloy be made up of them.
6. metallurgy according to claim 5 is with the cored-wire of v n micro alloying and complex deoxidization; It is characterized in that: described deoxidation nitrogen fixation agent also can include in titanium, zirconium, niobium, manganese, chromium, silicon, carbon and the iron one or more except the alloy that contains at least a metallic aluminium, calcium, magnesium, barium or be made up of them.
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| CN110343951B (en) * | 2019-06-27 | 2021-06-29 | 江苏省沙钢钢铁研究院有限公司 | 600 MPa-level large-deformation-resistant reinforcing steel bar and production method thereof |
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| CN111826498A (en) * | 2020-07-31 | 2020-10-27 | 唐山飞迪冶金材料有限公司 | Additive for increasing strength of deformed steel bar and preparation method and application thereof |
| CN113293332A (en) * | 2021-06-04 | 2021-08-24 | 马鞍山市兴达冶金新材料有限公司 | Product and method for direct vanadium alloying of molten steel |
| CN114000040A (en) * | 2021-11-19 | 2022-02-01 | 甘肃酒钢集团宏兴钢铁股份有限公司 | Production method for improving nitrogen content in vanadium microalloyed deformed steel bar |
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