CN102031441B - Complex additive for spheroidizing and dispersing sulfides in steel and use method thereof - Google Patents
Complex additive for spheroidizing and dispersing sulfides in steel and use method thereof Download PDFInfo
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- CN102031441B CN102031441B CN2010105286647A CN201010528664A CN102031441B CN 102031441 B CN102031441 B CN 102031441B CN 2010105286647 A CN2010105286647 A CN 2010105286647A CN 201010528664 A CN201010528664 A CN 201010528664A CN 102031441 B CN102031441 B CN 102031441B
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Abstract
The invention relates to a complex additive for spheroidizing and dispersing sulfides in steel and a use method thereof. The invention adopts the technical scheme that the complex additive comprises the following chemical components in percentage by weight: 30-65wt% of Si, 5-15wt% of Ca, 5-25wt% of Ti, 10-35wt% of Zr, 10-35wt% of Nd and the balance Fe and inevitable impurities. The complex additive is prepared by adding Ti, Zr and Nd on the basis of Si-Ca alloy according to the components by smelting and casting in a vacuum induction furnace. The use method of the complex additive comprises the following steps: before the complex additive is added, keeping the content of the free oxygen in molten steel to be 10-300ppm, then carrying out deoxidization and complex alloying by the complex additive, and adding the complex additive into the molten steel in a form of blocky alloy or core-spun yarn, wherein the additive amount is 0.5-5kg per ton of steel. The invention has the characteristics of low cost, simple technical process and high component hit rate. The steel which is rolled after being smelted by the complex additive has good toughness, processing performance and cutting performance.
Description
Technical field
The invention belongs to technical field of smelting.Relate in particular to a kind of nodularization of steel sulfide and dispersive composite additive and method of use of being used for.
Background technology
As everyone knows, the unit of the machinability of raising steel have S, Pb, Se, Te, Bi, Ca, Ti etc.What develop the earliest is the free-cutting steel that adds sulphur.The U.S. uses it for auto parts since nineteen twenty, and Japan is before and after 1940, and this steel grade comes across the JES standard, and nineteen fifty-two is included the JIS standard in.The compound series free-cutting steel of elements such as sulphur free-cutting steel and S, P, N, Pb is referred to as resulfurizing series free cutting steel, can be divided into by purposes: sulphur system and the multiple platform series free-cutting steel of sulfur-bearing of paying attention to machinability; Attach most importance to and the physical construction that increases free-cutting machinability is used resulfurizing series free cutting steel with mechanical property.The effect of MnS raising machinability is following: (1) stress concentration source, and (2) lubrication, (3) suppress the built-up edge effect, and (4) alleviate friction.In order to improve machinability, it is also conceivable that to add P, Pb, Te, Bi etc.For steel for mechanical structure,, in molten steel, add aluminium, and wherein a part of aluminium is with Al for purity and the adjustment grain fineness number that improves steel
2O
3Form remain in the steel.Because Al
2O
3Stone, with sintered carbide tools or cermet tool cutting the time, can increase loss because of friction.
For general structure steel grade, at room temperature sulfide is little to the intensity effect of steel in the steel, but its content and form but have very big influence to toughness (like the relative reduction in area and the impelling strength etc.), particularly low-temperature flexibility of steel.Concerning most of steel grades, sulphur content increases the performance that can reduce steel.Under hot processing temperature, the MnS inclusion is easy to be extended into strip, thereby causes steel flexible anisotropy.Sulfide inclusion is formed product performance is also had a significant effect, and manganese sulfide inclusion is easy to distortion when rolling, sulfurated lime more firmly, in fact indeformable in rolling.The possibility that sulfide has generation hydrogen to bring out crackle.Because the MnS that hydrogen is easy to be elongated is mingled with trapping, and makes it alleviate the resistibility of hydrogen being brought out crackle.The weldableness of steel, workability, mechanicalness etc. also receive the influence of the type and the quantity of sulfide inclusion in the steel.The sulfide that is netted existence in the steel can cause the red brittleness of steel.
Can find out by above-mentioned analysis: no matter be the sulfide favourable,, all must form, size and the distribution of sulfide be control effectively, could produce favourable effect and effect still to the disadvantageous sulfide of toughness to free-cutting steel.
The unit that can play spheroidization to sulfide have following several kinds:
(1) calcium: calcium can have precedence over manganese and combine with sulphur to form sulfurated lime in steel, manganese sulfide and sulfurated lime are dissolving each other more than 1170 ℃ fully.Dissolved calcium amount is higher more spherical in the manganese sulfide, is random distribution.In steelmaking process, add calcium treatment stage of molten steel, form CaS (Ca, Mn) S.
(2) tellurium: solid solution is in manganese sulfide slightly for tellurium, and while tellurium manganese often is eutectic growth with manganese sulfide and is in the same place.Manganese sulfide behind the solid solution tellurium and manganese sulfide-tellurium manganese two is inclusion mutually, all is spherical.The MnTe that around MnS, separates out plays a part sliding slightly property epithelium when hot rolling, suppress the solid deformation of MnS, forms elliposoidal, and the tellurium free-cutting steel also is except that improving the tool performance and the cold-forming property, being prolonged in the TS life-span significantly.Selenium also has and similar function of tellurium and effect.
(3) magnesium: magnesium also has the effect of nodularization sulfide.But its inconvenience adds in the steel, so in industrial production, do not obtain practical application as yet.
(4) rare earth: REE is stronger than manganese with the avidity of sulphur, can replace manganese and form RES, and the solid solubility of REE in manganese sulfide is very high simultaneously, and the manganese sulfide of RES and solid solution rare earth becomes spherical more.
Above-mentioned magnesium, rare earth, calcium, the solid solubility of four kinds of elements of tellurium in iron matrix are all very low.It is that the sulfide of these elements is low to the wettability of steel matrix that these elements can make the reason of sulfide nodularization, and interfacial energy is high, and contact angle is big, so glomeration.
In order to improve the cutting ability of steel, except aforesaid method, also have following method:
(1) lead: be insoluble in the steel because of lead, but be distributed in the tip of MnS inclusion in the steel matrix neutralization with the fine particulate disperse.For the machinability that improves steel requires the minimum lead content in the steel is 0.35%.
(2) bismuth: bismuth is nontoxic element. can be used to replace plumbous the adding in the free-cutting steel.The density of bismuth is plumbous little, more approaches iron, this means that the segregation degree of bismuth in molten steel is lower than lead.Adopt bismuth to replace sulphur and plumbous, can not damage the mechanical property of steel, also do not have pollution problem as the interpolation element that improves machinability.
But there is following shortcoming in above-mentioned the whole bag of tricks:
One, the steel of handling for calcium
Aspect cutting force, do not have significant difference between conventional steel and the calcium treated steel, and do not having difference aspect cutting handlability and the surface smoothness yet with basic steel; In addition, the adding mode more complicated of calcium: the one, in ladle, in molten steel, add calcium with gunite through spray gun; Another kind is to add calcium with bag core wire feeding method.
Two, the steel of handling for tellurium and selenium
(1) these two kinds of element prices are all very high; (2) all has toxicity; (3) tellurium also can cause red brittleness when rolling.
Three, the steel of handling for magnesium
Because magnesium is very light, be difficult to when adding molten steel separately add, and yield is low.
Four, the steel of handling for rare earth
(1) rare earth is easy to generate radioactive dust in the process of producing and using, and the radiological hazard of generation can not be ignored; The mouth of a river was prone to dross when (2) steel of rare earth processing was poured into a mould, and during with strong reductor such as A1 deoxidation, the nozzle clogging problem also often occurred; (3) re inclusion generally between 5.5～6.5, is difficult for come-up than great; Particularly add when excessive when rare earth, can increase harmful being mingled with in the steel, particularly large size is mingled with; Even produce the intermetallic compound of brittle rare earth and iron, worsen the performance of steel; (4) price of rare earth metal is more expensive.
Five, the steel of handling for lead
Because plumbous density is higher, and the solubleness in steel is very little, thus the tendency of past steel ingot bottom segregation is arranged, so that cause and can't estimate plumbous yield.In addition, lead and plumbous oxide are all poisonous.
Six, the steel of handling for bismuth
Because it is the bismuth price is high, economical inadequately as the additive that improves machinability.In addition, the effective means that adds bismuth in the steel is in the steel flow of casting, to spray the bismuth ball, and the adding mode is complicacy.
Summary of the invention
The present invention is intended to overcome the prior art defective, and purpose provides a kind of with low cost and technology and simply is used for nodularization of steel sulfide and dispersive composite additive.This composite additive spheriodizing technique is simple, smelts after rolling steel good toughness, good processability and excellent cutting performance with this composite additive.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is: the chemical ingredients and the content thereof of this additive are: Si is 30～65wt%, and Ca is 5～15wt%; Ti is 5～25wt%; Zr is 10～35wt%, and Nd is 10～35wt%, and all the other are Fe and unavoidable impurities; Its preparation method is: press mentioned component, be the basis with the Si-Ca alloy, add Ti, Zr and Nd; Form through vacuum induction melting and casting.
Wherein: Ti is to be the Ti alloy that raw material forms through refinement with Ti magnetite blast furnace slag; Zr is sponge grease Zr or for the Si-Zr alloy or for metallic Z r; Nd is metal Nd or is the Fe-Nd alloy.
The method of use of the composite additive of the present invention preparation is: adopt converter or electric arc furnace that molten iron or steel scrap or molten iron are carried out refining and adjust molten steel composition with steel scrap after steel-making; Before adding composite additive, keeping the free oxygen level in the molten steel is 10～300ppm; Carry out deoxidation and composite alloying with composite additive again; Composite additive adds molten steel with the form of bulk alloy or cored-wire, and add-on is steel 0.5～5kg per ton, carries out continuous casting and hot rolling by common process then.
Because adopt technique scheme, the present invention is a staple with Si, Ca, Ti, Zr and Nd, form through vacuum induction melting and casting, so have with low cost, technological process is simple.The prepared composite additive helps the composite sulfur oxide compound of sulfide nodularization; For thinning microstructure favourable forming core particle is provided simultaneously; The form that a plurality of elements are made alloy or cored-wire according to the ratio that helps the sulfide nodularization adds the once task of accomplishing sulfide nodularization and structure refinement.So technological process of the present invention is simple, activity time short (once accomplishing deoxidation and alloying), composition shoots straight.
Because tiny, the dispersion, spherical in shape of sulfide that exists in the steel, so its good toughness, good processability and excellent cutting performance, the HSLA tensile strength of manufacturing is 500～900MPa.The present invention is applicable to the high HSLAs of toughness reguirements such as large scale structure, equipment, facility such as crude oil storage tank, construction(al)steel, boats and ships warship, especially is suitable for low carbon-sulfur easy-cutting high strength steel, physical construction with sulfur-bearing easy-cutting high strength steel.
Embodiment
Below in conjunction with embodiment the present invention being further described, is not the restriction to its protection domain.
For avoiding repetition, earlier the Ti that is added in the embodiment, Zr and Nd are described below respectively, repeat no more among the embodiment: Ti is to be the Ti alloy that raw material forms through refinement with Ti magnetite blast furnace slag; Zr is sponge grease Zr or for the Si-Zr alloy or for metallic Z r; Nd is metal Nd or is the Fe-Nd alloy.
Embodiment 1
A kind of nodularization of steel sulfide and dispersive composite additive and method of use of being used for.The chemical ingredients and the content thereof of this composite additive are: Si is 30～50wt%, and Ca is 10～15wt%, and Ti is 13～25wt%, and Zr is 20～25wt%, and Nd is 15～35wt%, and all the other are Fe and unavoidable impurities.
The preparation method of this composite additive is: press mentioned component, be the basis with the Si-Ca alloy, add Ti, Zr and Nd; Form through vacuum induction melting and casting.
The deoxidation of present embodiment and the technology of compound composite alloying are: adopt converter or electric arc furnace that molten iron is carried out refining and adjustment molten steel composition after steel-making; Before adding composite additive, keeping the oxygen level in the molten steel is 10～120ppm; Carry out deoxidation and composite alloying with composite additive then, composite additive adds molten steel with the bulk alloy form, and add-on is steel 0.5～1.5kg per ton; Carry out continuous casting and hot rolling by common process at last, be cast into the strand that thickness is 250mm.
The strand chemical ingredients and the content thereof of present embodiment are: C is 0.03～0.07wt%, and Si is 0.1～0.3wt%, and Mn is 1.5～2.5wt%; Ni is 0.2～0.6wt%, and Cu is 0.6～1.0wt%, and Als is 0.02～0.06wt%; Nb is 0.03～0.07wt%, and Ca is 0.0001～0.0005wt%, and Ti is 0.01～0.05wt%; Zr is 0.0001～0.030wt%, and N is 0.006～0.010wt%, and B is 0.001～0.002wt%; S is 0.005～0.015wt%, P＜0.008wt%, and all the other are Fe and unavoidable impurities.
Hot rolling technology is, strand is heated to 1150～1250 ℃, and hot rolling was carried out in soaking in 2～3 hours, and rolling is the thick steel plate of 40～60mm; Carry out online cooling with the speed of cooling of 5～15 ℃/s then.
The tensile strength of rolling low-alloy high-strength steel plate be 500～700MPa, the sulfide in the steel is small and dispersed and distributes, its size is 200～500 nanometers; The steel plate tenacity excellent, the ballistic work of v-notch-40 ℃ is greater than 300J, and-60 ℃ ballistic work is greater than 200J; This steel plate also can bear the large-line energy welding of 150～400kJ/cm, need not heat-treat after the welding, has good welding property, and the ballistic work of its welded heat affecting zone is not less than 2/3 of mother metal ballistic work.
Embodiment 2
A kind of nodularization of steel sulfide and dispersive composite additive and method of use of being used for.The chemical ingredients and the content thereof of this composite additive are: Si is 35～60wt%, and Ca is 7～12wt%, and Ti is 5～14wt%, and Zr is 12～20wt%, and Nd is 10～20wt%, and all the other are Fe and unavoidable impurities.
The preparation method of this composite additive is: press mentioned component, be the basis with the Si-Ca alloy, add Ti, Zr and Nd; Form through vacuum induction melting and casting.
The deoxidation of present embodiment and the technology of alloying are: adopt electric arc furnace that steel scrap is carried out refining and adjustment molten steel composition after steel-making; Before adding composite additive, keeping the oxygen level in the molten steel is 120～200ppm; Carry out deoxidation and composite alloying with composite additive then, composite additive adds molten steel with the bulk alloy form, and add-on is steel 1～3kg per ton; Carry out continuous casting by common process at last, casting becomes the square billet of 150mm.
The chemical ingredients and the content thereof of present embodiment strand are: C is 0.08～0.60wt%, and Si is 0.05～1.0wt%, and Mn is 0.2～2.5wt%; Als is 0.01～0.06wt%, and Ca is 0.0001～0.0005wt%, and Ti is 0.01～0.05wt%; Zr is 0.01～0.1wt%, and Nd is 0.01～0.4wt%, and S is 0.03～0.40wt%; N is 0.004～0.008wt%, P＜0.10wt%, and all the other are Fe and unavoidable impurities.
Hot rolling technology is, earlier strand is heated to 1250～1350 ℃, and hot rolling is carried out in soaking 1.5～2.5 hours again, and rolling is the wire rod of 6.5mm for diameter.
The tensile strength of the wire rod of manufacturing is 600～800MPa, owing to adopt above-mentioned technology, the MnS in the steel is small and dispersed and distributes, and its particle diameter is 200～800 nanometers, and its cutting ability is good.
Embodiment 3
A kind of nodularization of steel sulfide and dispersive composite additive and method of use of being used for.The chemical ingredients and the content thereof of this composite additive are: Si is 40～65wt%, and Ca is 5～10wt%, and Ti is 5～15wt%, and Zr is 13～35wt%, and Nd is 10～30wt%, and all the other are Fe and unavoidable impurities.
The preparation method of this composite additive is: press mentioned component, be the basis with the Si-Ca alloy, add Ti, Zr and Nd, form through vacuum induction melting and casting.
The deoxidation of present embodiment and the technology of composite alloying are: adopt converter that molten iron and steel scrap are carried out refining and adjustment molten steel composition after steel-making; Before adding composite additive, keeping the oxygen level in the molten steel is 150～300ppm; Carry out deoxidation and composite alloying with composite additive then, composite additive adds molten steel with the form of cored-wire, and add-on is steel 2.5～5kg per ton; Carry out continuous casting by common process at last, be cast into the square billet of 150mm.
The chemical ingredients and the content thereof of present embodiment strand are: C is 0.02～0.2wt%, and Si is 0.1～0.3wt%, and Mn is 0.5～3.0wt%; Als is 0.0001～0.005wt%, and Ca is 0.0001～0.0005wt%, and Ti is 0.01～0.05wt%; Zr is 0.1～0.3wt%, and Nd is 0.1～0.3wt%, and S is 0.2～0.5wt%; P is 0.02～0.2wt%, and N is 0.002～0.010wt%, and all the other are Fe and unavoidable impurities.
Hot rolling technology is, strand is heated to 1250～1350 ℃, and hot rolling is carried out in soaking 1.5～2.5 hours, and rolling is the wire rod of 6.5mm for diameter.
The tensile strength of the wire rod of present embodiment manufacturing is 700～900MPa, owing to adopt above-mentioned technology, the MnS in the steel is small and dispersed and distributes, and its particle diameter is 200～1200 nanometers, and its cutting ability is good.
This embodiment is a staple with Si, Ca, Ti, Zr and Nd, through vacuum induction melting and the casting form, so have with low cost, technological process is simple.The prepared composite additive helps the composite sulfur oxide compound of sulfide nodularization; For thinning microstructure favourable forming core particle is provided simultaneously; Form in a plurality of elements are made alloy or cored-wire according to the ratio that helps the sulfide nodularization adds the once task of accomplishing sulfide nodularization and structure refinement.So this embodiment technological process is simple, activity time short (once accomplishing deoxidation and alloying), composition shoots straight.
Because tiny, the dispersion, spherical in shape of sulfide that exists in the steel, so its good toughness, good processability and excellent cutting performance, the HSLA tensile strength of manufacturing is 500～900MPa.This embodiment can extensively be suitable for the high HSLAs of toughness reguirements such as large scale structure, equipment, facility such as crude oil storage tank, construction(al)steel, boats and ships warship.Especially be suitable for low carbon-sulfur easy-cutting high strength steel, physical construction with sulfur-bearing easy-cutting high strength steel.
Claims (5)
1. one kind is used for nodularization of steel sulfide and dispersive composite additive; The chemical ingredients and the content thereof that it is characterized in that this composite additive are: Si is 30～65wt%; Ca is 5～15wt%, and Ti is 5～25wt%, and Zr is 10～35wt%; Nd is 10～35wt%, and all the other are Fe and unavoidable impurities; The preparation method of this composite additive is: press mentioned component, be the basis with the Si-Ca alloy, add Ti, Zr and Nd; Form through vacuum induction melting and casting.
2. nodularization of steel sulfide and the dispersive composite additive of being used for according to claim 1 is characterized in that Ti is is the Ti alloy that raw material forms through refinement with Ti magnetite blast furnace slag.
3. nodularization of steel sulfide and the dispersive composite additive of being used for according to claim 1 is characterized in that Zr is the Si-Zr alloy or is metallic Z r.
4. nodularization of steel sulfide and the dispersive composite additive of being used for according to claim 1 is characterized in that Nd is metal Nd or is the Fe-Nd alloy.
5. like the described method of use that is used for nodularization of steel sulfide and dispersive composite additive of claim 1 ~ 4; It is characterized in that adopting converter or electric arc furnace that molten iron or steel scrap or molten iron and steel scrap are carried out refining and adjustment molten steel composition after steel-making; Before adding composite additive, keeping the free oxygen level in the molten steel is 10～300ppm; Carry out deoxidation and composite alloying with composite additive again; Composite additive adds molten steel with the form of bulk alloy or cored-wire, and add-on is steel 0.5 ~ 5kg per ton, carries out continuous casting and hot rolling by common process then.
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| CN102199683B (en) * | 2011-05-17 | 2012-10-03 | 武汉钢铁(集团)公司 | Rapid desulfurizing method for smelting ultrapure steel with vacuum induction furnace |
| CN107385149A (en) * | 2017-06-27 | 2017-11-24 | 苏州楚博生物技术有限公司 | A kind of silico-calcium cored core powder |
| CN109971918B (en) * | 2019-04-09 | 2021-01-12 | 上海大学 | Bismuth-tellurium composite adding process method for free-cutting steel |
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