CN102248141A - High-alkalinity mould flux used for niobium/vanadium/titanium-containing low alloy wide and heavy plate blank and manufacturing method thereof - Google Patents
High-alkalinity mould flux used for niobium/vanadium/titanium-containing low alloy wide and heavy plate blank and manufacturing method thereof Download PDFInfo
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- CN102248141A CN102248141A CN201110175156XA CN201110175156A CN102248141A CN 102248141 A CN102248141 A CN 102248141A CN 201110175156X A CN201110175156X A CN 201110175156XA CN 201110175156 A CN201110175156 A CN 201110175156A CN 102248141 A CN102248141 A CN 102248141A
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Abstract
The invention discloses a high-alkalinity mould flux used for niobium/vanadium/titanium-containing low alloy wide and heavy plate blanks and a manufacturing method thereof. The high-alkalinity mould flux is made from the following raw materials in percentage by weight: 35 to 45 percent of pre-melting materials, 11 to 14 percent of fluorite, 28 to 30 percent of wollastonite, 3 to 6 percent of flint clay, 3 to 6 percent of limestone, 2 to 4 percent of sodium carbonate, 1 to 3 percent of lithium carbonate, 1 to 3 percent of manganese carbonate, 2 to 4 percent of magnesium oxide, 2 to 4 percent of carbon black, 4 to 7 percent of graphite and 1 to 3 percent of binders. The mould flux has a good capability of absorbing Al (s), V, Ti, Nb and other metals and metal oxides or carbides thereof and nitride inclusions in molten steel, and remains unchanged after molten steel purification. Therefore, not only are the performances of the mould flux stable, but also the internal quality of casting blanks is improved.
Description
Technical field
The invention belongs to steel-making is the crystallizer protecting residue technical field with auxiliary material, and particularly a kind of niobium, vanadium, Ti low alloyed generous slab of containing is with high basicity crystallizer protecting residue and manufacture method thereof.
Technical background
Vanadium, titanium, niobium alloy is as adding element, in steel, form tiny carbide and nitride or carboritride, its particle is pinned at the crystal boundary place, heating and can stop growing up and the austenitic crystallization again of deformation of austenite crystal in the crystallization controlled rolling process again, delay growing up of crystallization austenite crystal again, in welding process, stop the alligatoring of welding heat affected zone crystal grain, thereby significantly improve its yield strength and toughness, also have good cold and hot working performance and welding performance simultaneously, since 1980, China has developed the Ti low alloyed steel of a series of niobium vanadium according to the national economy needs, as the oil pipeline steel, bridge steel, boiler steel, offshore drilling platform steel etc., obtained using widely, while China's vanadium, titanium, niobium alloy element reserves are abundant, so China has the development vanadium, titanium, the huge resources advantage of niobium low alloying steel.
Contain in niobium, vanadium, the Ti low alloyed generous slab process at continuous casting, the face crack incidence of this type of steel is significantly higher than common straightcarbon steel, it is the highest wherein to contain niobium steel crack sensitivity, and the breed structure steel and the advanced country in the world gap of China are very far away, and this has seriously restricted the development of China's steel alloy.
The defective that contains niobium, vanadium, the generous slab of titanium mainly is surperficial lobe and transverse corner crack line.One; after the covering slag melt cinder absorbs metal such as Al (s) in the molten steel, V, Ti, Nb and oxide thereof or carbide, nitride; bigger variation can take place in characteristics such as viscosity; change the heat flow density of crystallizer bight copper coin; significantly worsen the cooling and the lubricating condition of initial solidification shell; cause frictional force to increase and stress concentrated, two cold expansions and produce transverse corner crack.They are two years old, casting blank section is thick and wide, the steel grade that waters is again that the bigger middle carbon of slab caster top casting difficulty contains niobium, vanadium, titanium alloy steel, the solidification shrinkage amount is big, and the base shell can break away from crystallizer wall when the solidified shell amount of contraction is big, causes the minimizing of crystallizer hot-fluid and conducts heat inhomogeneous, stress increases, produce depression at weakness, the hysteresis of base shell local solidification can cause surface longitudinal crack, and the increase along with width of plate slab simultaneously exists center segregation to add reconstructed image again.Therefore, select to use high basicity, low viscosity, high crystalline can covering slag, the absorption that improves covering slag is mingled with ability, prevents the melt cinder sex change, the slag bar is thin and need not to choose the slag bar for a short time; Melt cinder imports evenly, and crystallizer conducts heat evenly, frictional force is less, and the even slow cooling of base shell is avoided surface crack defect thereby reach.
Summary of the invention
The object of the present invention is to provide a kind of can solve surperficial lobe and transverse corner crack line defective well contain niobium, vanadium, Ti low alloyed generous slab with high basicity crystallizer protecting residue and manufacture method thereof.
A kind of niobium, vanadium, Ti low alloyed generous slab of containing with high basicity crystallizer protecting residue, its raw material components by weight percentage is: (its composition and percentage by weight consist of pre-melt: SiO
242～45%, CaO 36～39%, MgO 1.5～3.5%, Fe
2O
3Be not more than 1%, Al
2O
34～6%, Na
2O 5～7%, F 2～4%) 35～45%, fluorite 11～14%, wollastonite 28～30%, flint clay 3～6%, lime stone 3～6%, sodium carbonate 2～4%, lithium carbonate 1～3%, manganese carbonate 1～3%, magnesia 2～4%, carbon black 2～4%, graphite 4～7%, binding agent 1～3%.
The chemical composition quality per distribution ratio of described crystallizer protecting residue is as follows: CaO 38～45%, SiO
220～27%, MgO 1～3%, Al
2O
33～5%, Fe
2O
30.75～0.96%, Na
2O 4～7%, Li
2O 1～3%, F
-7～9%, MnO 1～4%, solid carbon 5～8%, and surplus is a fugitive constituent.
The chemical composition quality per distribution ratio of described crystallizer protecting residue is as follows: CaO 41%, SiO
225%, MgO 2%, Al
2O
34%, Fe
2O
30.93%, Na
2O 5.5%, Li
2O 2%, F
-8%, MnO 2.5%, solid carbon 7%, and surplus is a fugitive constituent.
The niobium, vanadium, Ti low alloyed generous slab of containing of the present invention mainly considered following factor with high basicity crystallizer protecting residue:
1. the basicity of covering slag and viscosity
Covering slag basicity is the index of reflection melt structure, to the crystallization property of covering slag and covering slag to solidify behavioral implications very big, be directly connected to the heat conductivility and the greasy property of covering slag, be the important indicator of weighing the covering slag characteristic.Covering slag basicity directly influences the percent crystallization in massecuite of slag film; high basicity slag can form the slag film of high percent crystallization in massecuite; the covering slag of high percent crystallization in massecuite is beaten and can effectively be reduced and control strand through the heat transfer of slag film to crystallizer; make the casting blank shell growth evenly; avoid crackle to produce; particularly contain niobium, vanadium, Ti low alloyed generous slab, crack sensitivity is strong, and covering slag will have higher basicity.
Using common covering slag casting to contain in the low-alloy processes such as niobium, vanadium, titanium; after the covering slag melt cinder absorbs metal such as Al (s) in the molten steel, V, Ti, Nb and oxide thereof or carbide, nitride; bigger variation can take place in characteristics such as viscosity; change the heat flow density of crystallizer bight copper coin; significantly worsen the cooling and the lubricating condition of initial solidification shell; cause frictional force to increase and stress is concentrated, two cold expansions and produce transverse corner crack produce consequently surperficial lobe of depression at weakness.Therefore, use the covering slag of high basicity, low viscosity, high crystalline energy, the absorption that improves covering slag is mingled with ability and prevents its sex change; the slag bar is thin and little, need not to choose the slag bar, and melt cinder imports evenly; the all even greasy property of conducting heat is good, and blemish is avoided in the even slow cooling of base shell.
High basicity covering slag helps controlling conducting heat and absorbing and is mingled with the back consistency in the molten steel, the basicity (CaO/SiO that contains niobium, vanadium, Ti low alloyed generous slab with high basicity crystallizer protecting residue therefore of the present invention
2) scope of design is 1.3～1.5, fusion temperature is 1150～1170 ℃, 1130 ℃ of viscosity are 0.08～0.15PaS.
2. pre-melt
The performance of covering slag depends on the selection of making slag charge, and conventional machine mixes slag and mainly adopts multiple raw material to be mixed and made into, and produces a large amount of gases because decompose the back that is heated, and slag blanket stirs acutely, and this has influenced the stability of slag.The present invention selects for use the pre-melted type slag to join the slag base-material as covering slag, and the auxiliary slag charge that suitably is equipped with chance pyrolytic release gas makes covering slag not only keep the active of solid-state slag blanket but also can keep the stable of melt cinder in fusion process to improve its activity.The pre-melt of high basicity crystallizer protecting residue of the present invention is chosen in 35～45% scopes by weight.
3. carbonaceous material
Graphite in the carbonaceous material and carbon black have good skeleton function, reasonably join carbon the various batchings in the covering slag are uniformly dispersed, and the control burn-off rate is avoided fractional melting.The type of covering slag burn-off rate and carbonaceous material, mass fraction, particle diameter and join the carbon mode direct relation is arranged.Mass fraction increase along with carbonaceous material in the covering slag, burn-off rate reduces gradually, under low quality was divided said conditions, granularity was less, decentralization is big, ignition point is lower, surface free energy is higher, and the active carbon of impalpable structure and carbon black have the good isolation effect; Under high-quality divided said conditions, granularity was big, decentralization is less, ignition point is higher, surface free energy is lower, and the graphite of laminated structure has good skeleton function.Therefore the control range of determining carbon content in the covering slag is 3～6%, and wherein semi-reinforcing carbon black 2～4%, flaky graphite 4～7%.
The manufacture method of continuous crystallizer protecting slag of the present invention comprises the following steps:
1. by weight percentage clinker, fluorite powder, white alkali etc. are prepared burden, stir, make ball, drying, the mixing ball that makes, moisture content≤5%.
2. will prepare the white by weight percentage alkali of the required basic slag charge of the pre-melt of covering slag, fluorite, lime stone, wollastonite, glass, coke and fully mix the back roasting and melt by the mixing ball that above-mentioned steps 1 makes; carry out shrend again; drying is handled to moisture≤0.5%; ball milling; sieve back granularity 400 orders more than 96%, get the pre-melt of covering slag.
3. according to the concrete proportioning of this steel grade covering slag; pre-melt, auxiliary material, binding agent, carbonaceous material are prepared burden by 600Kg; going into ball mill fully mixes; water mill slurrying; water mill time 〉=50min, mist projection granulating in the hydraulic pump input spray drying tower, pump pressure 1.2～1.6MPa; 580～660 ℃ of tower body intake air temperatures, 150～200 ℃ of air outlet temperature.Afterwards 500 orders are more than 90% in order to sieve for described auxiliary material spherolite degree, and described carbonaceous material can be a carbon black, black or its mixture of stone.
4. an above-mentioned gained pre-melted type hollow covering slag material is advanced screening, the particle of the back granularity 0.20～1.0mm that sieves is more than 95%, moisture content≤0.3%.
This covering slag has the ability of metals such as Al (s) in the good absorption molten steel, V, Ti, Nb and field trashes such as oxide or carbide, nitride thereof; covering slag still maintains the invariance behind purify hot metal, has not only guaranteed the stable performance of covering slag but also has improved the internal soundness of strand.In use the slag bar is thin and little for this covering slag, need not to provoke the slag bar, thereby it is even, smooth and easy to guarantee that liquid slag imports, and effectively control is conducted heat and reduced frictional force, avoids the generation of face crack, improves the external mass of strand.Use this covering slag at certain 220 * 2065～2665mm of steel mill
2When the conticaster top casting of section contains niobium, vanadium, Ti low alloyed steel; casting rate 1.0～1.2m/min; prove through field trial; this covering slag in use covering slag spreadability is good; molten state and heat-insulating property are good, and the slag consumption is 0.43～0.46Kg/t steel, liquid slag layer thickness 8～12mm; the steady ripple disable of heat flow curve, crystallizer heat flux 1.1～1.3MW/m
2, crystallizer frictional force 13～15KN/m
2Slag slag bar is thin and little, need not to provoke the slag bar, and casting billet surface does not have slag inclusion, depression and crackle, and surface quality is intact; Rolling back carrying out flaw detection does not have and is mingled with.
The specific embodiment
Embodiment 1:
A kind of niobium, vanadium, Ti low alloyed generous slab of containing with high basicity crystallizer protecting residue, its raw material components by weight percentage is: (its composition and percentage by weight consist of pre-melt: SiO
242～45%, CaO 36～39%, MgO 1.5～3.5%, Fe
2O
3Be not more than 1%, Al
2O
34～6%, Na
2O 5～7%, F 2～4%) 35～45%, fluorite 11～14%, wollastonite 28～30%, flint clay 3～6%, lime stone 3～6%, sodium carbonate 2～4%, lithium carbonate 1～3%, manganese carbonate 1～3%, magnesia 2～4%, carbon black 2～4%, graphite 4～7%, binding agent 1～3%.
The chemical composition quality per distribution ratio of described crystallizer protecting residue is as follows: CaO 40.94%, SiO
227.60%, Li
2O 1.72%, and NaO 4.82%, F
-8.68%, MgO 1.55%, Al
2O
34.12%, Fe
2O
30.93%, MnO 1.62%, solid carbon C 7.08%.Covering slag physical property: basicity (CaO/SiO
2) 1.48,1165 ℃ of fusing points, viscosity (1300 ℃) 0.09PaS, burn-off rate 20 seconds.
Embodiment 2:
A kind of niobium, vanadium, Ti low alloyed generous slab of containing with high basicity crystallizer protecting residue, its raw material components by weight percentage is: (its composition and percentage by weight consist of pre-melt: SiO
242～45%, CaO 36～39%, MgO 1.5～3.5%, Fe
2O
3Be not more than 1%, Al
2O
34～6%, Na
2O 5～7%, F 2～4%) 35～45%, fluorite 11～14%, wollastonite 28～30%, flint clay 3～6%, lime stone 3～6%, sodium carbonate 2～4%, lithium carbonate 1～3%, manganese carbonate 1～3%, magnesia 2～4%, carbon black 2～4%, graphite 4～7%, binding agent 1～3%.
The chemical composition quality per distribution ratio of described crystallizer protecting residue is as follows: CaO 37.14%, SiO
227.11%, Li
2O 1.72%, and NaO 4.82%, F
-8.68%, MgO 1.55%, Al
2O
34.12%, Fe
2O
30.95%, MnO 1.32%, Gu C 8.11%.Covering slag physical property: basicity (CaO/SiO
2) 1.37,1165 ℃ of fusing points, viscosity (1300 ℃) 0.14PaS, burn-off rate 22 seconds.
Embodiment 3:
A kind of niobium, vanadium, Ti low alloyed generous slab of containing with high basicity crystallizer protecting residue, its raw material components by weight percentage is: (its composition and percentage by weight consist of pre-melt: SiO
242～45%, CaO 36～39%, MgO 1.5～3.5%, Fe
2O
3Be not more than 1%, Al
2O
34～6%, Na
2O 5～7%, F 2～4%) 35～45%, fluorite 11～14%, wollastonite 28～30%, flint clay 3～6%, lime stone 3～6%, sodium carbonate 2～4%, lithium carbonate 1～3%, manganese carbonate 1～3%, magnesia 2～4%, carbon black 2～4%, graphite 4～7%, binding agent 1～3%.
The chemical composition quality per distribution ratio of described crystallizer protecting residue is as follows: CaO 41%, SiO
225%, MgO 2%, Al
2O
34%, Fe
2O
30.93%, Na
2O 5.5%, Li
2O 2%, F
-8%, MnO 2.5%, solid carbon 7%, and surplus is a fugitive constituent.Covering slag physical property: basicity (CaO/SiO
2) 1.64,1164 ℃ of fusing points, viscosity (1300 ℃) 0.14PaS, burn-off rate 21 seconds.
Claims (3)
1. one kind contains niobium, vanadium, Ti low alloyed generous slab with high basicity crystallizer protecting residue and manufacture method thereof, it is characterized in that its raw material components by weight percentage is: (its composition and percentage by weight consist of pre-melt: SiO
242～45%, CaO 36～39%, MgO 1.5～3.5%, Fe
2O
3Be not more than 1%, Al
2O
34～6%, Na
2O 5～7%, F 2～4%) 35～45%, fluorite 11～14%, wollastonite 28～30%, flint clay 3～6%, lime stone 3～6%, sodium carbonate 2～4%, lithium carbonate 1～3%, manganese carbonate 1～3%, magnesia 2～4%, carbon black 2～4%, graphite 4～7%, binding agent 1～3%.
2. niobium, vanadium, the Ti low alloyed generous slab of containing as claimed in claim 1 is characterized in that with high basicity crystallizer protecting residue the chemical composition quality per distribution ratio of described crystallizer protecting residue is as follows: CaO 38～45%, SiO
220～27%, MgO 1～3%, Al
2O
33～5%, Fe
2O
30.75～0.96%, Na
2O 4～7%, Li
2O 1～3%, F
-7～9%, MnO 1～4%, solid carbon 5～8%, and surplus is a fugitive constituent.
3. niobium, vanadium, the Ti low alloyed generous slab of containing as claimed in claim 2 is characterized in that with high basicity crystallizer protecting residue the chemical composition quality per distribution ratio of described crystallizer protecting residue is as follows: CaO 41%, SiO
225%, MgO 2%, Al
2O
34%, Fe
2O
30.93%, Na
2O 5.5%, Li
2O 2%, F
-8%, MnO 2.5%, solid carbon 7%, and surplus is a fugitive constituent.
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|---|---|---|---|
| CN 201110175156 CN102248141B (en) | 2011-06-27 | 2011-06-27 | High-alkalinity mould flux used for niobium/vanadium/titanium-containing low alloy wide and heavy plate blank and manufacturing method thereof |
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| CN104588601A (en) * | 2015-02-14 | 2015-05-06 | 河南通宇冶材集团有限公司 | High-speed wide and thick slab continuous casting mold flux |
| CN104624997A (en) * | 2015-03-04 | 2015-05-20 | 西峡龙成冶金材料有限公司 | Continuous casting mold flux for boron containing steel |
| CN104707958A (en) * | 2013-12-11 | 2015-06-17 | 宝山钢铁股份有限公司 | High-alkalinity continuous casting powder for casting peritectic steel |
| CN105344955A (en) * | 2015-12-18 | 2016-02-24 | 河南通宇冶材集团有限公司 | High-strength continuous casting crystallizer mold flux and preparing method thereof |
| CN105855492A (en) * | 2015-01-23 | 2016-08-17 | 鞍钢股份有限公司 | Method for suppressing corner cracks of boron-containing medium-carbon steel plate blanks |
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| CN108723314A (en) * | 2018-07-09 | 2018-11-02 | 西峡龙成冶金材料有限公司 | A kind of chamfer crystallizer low-alloy steel covering slag |
| CN110315039A (en) * | 2019-08-14 | 2019-10-11 | 中南大学 | A kind of application of Mold Powder Without Fluorine in Ti-containing steel continuous casting |
| CN112391541A (en) * | 2019-08-14 | 2021-02-23 | 山特维克材料技术公司 | Mold flux and method for manufacturing nickel-based alloy |
| CN112605355A (en) * | 2020-12-07 | 2021-04-06 | 西峡龙成冶金材料有限公司 | Special continuous casting crystallizer covering slag for heavy beam blank and application thereof |
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| CN114888249B (en) * | 2022-05-23 | 2024-05-10 | 首钢京唐钢铁联合有限责任公司 | Covering slag for producing medium carbon steel with high pulling speed of sheet billet and preparation method thereof |
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| CN104707958B (en) * | 2013-12-11 | 2017-08-25 | 宝山钢铁股份有限公司 | Casting peritectic steel high alkalinity continuous casting covering slag |
| CN105855492A (en) * | 2015-01-23 | 2016-08-17 | 鞍钢股份有限公司 | Method for suppressing corner cracks of boron-containing medium-carbon steel plate blanks |
| CN104588601A (en) * | 2015-02-14 | 2015-05-06 | 河南通宇冶材集团有限公司 | High-speed wide and thick slab continuous casting mold flux |
| CN104624997A (en) * | 2015-03-04 | 2015-05-20 | 西峡龙成冶金材料有限公司 | Continuous casting mold flux for boron containing steel |
| CN104624997B (en) * | 2015-03-04 | 2016-08-24 | 西峡龙成冶金材料有限公司 | A kind of boron-containing steel continuous crystallizer protecting slag |
| CN105344955A (en) * | 2015-12-18 | 2016-02-24 | 河南通宇冶材集团有限公司 | High-strength continuous casting crystallizer mold flux and preparing method thereof |
| CN107186186A (en) * | 2017-04-27 | 2017-09-22 | 甘肃酒钢集团宏兴钢铁股份有限公司 | A kind of method that CSP conticasters pour into a mould weather resisting steel |
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| CN108723314A (en) * | 2018-07-09 | 2018-11-02 | 西峡龙成冶金材料有限公司 | A kind of chamfer crystallizer low-alloy steel covering slag |
| CN110315039A (en) * | 2019-08-14 | 2019-10-11 | 中南大学 | A kind of application of Mold Powder Without Fluorine in Ti-containing steel continuous casting |
| CN110315039B (en) * | 2019-08-14 | 2020-09-29 | 中南大学 | Application of fluorine-free covering slag in titanium-containing steel continuous casting |
| CN112391541A (en) * | 2019-08-14 | 2021-02-23 | 山特维克材料技术公司 | Mold flux and method for manufacturing nickel-based alloy |
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| CN114888249A (en) * | 2022-05-23 | 2022-08-12 | 首钢京唐钢铁联合有限责任公司 | Covering slag for producing sheet billet high-drawing-speed medium carbon steel and preparation method thereof |
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