CN101947644A - High-manganese high-nitrogen low-nickel stainless steel plate blank continuous casting crystallizer covering slag and preparation method thereof - Google Patents
High-manganese high-nitrogen low-nickel stainless steel plate blank continuous casting crystallizer covering slag and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high-manganese high-nitrogen low-nickel stainless steel plate blank continuous casting crystallizer covering slag which comprises the following components in percentage by weight: 54-57% of wollastonite, 9-13% of fluorite, 9-13% of sodium carbonate, 0-1% of lithium carbonate, 5-7% of glass dust, 8-12% of vanadine soil, 2.5-2.7% of soot carbon and 3-3.5% of graphite, and comprises the chemical components in percentage by weight: 31.9-34.9% of calcium oxide, 32.1-35.1% of silicon dioxide, 7.3-8.3% of aluminium oxide, 0.5-1.5% of magnesium oxide, 0.5-1.4% of iron sesquioxide, 4.4-6.4% of fluorion, 6.5-7.5% of sodium oxide, 0-0.39% of lithium oxide, 4.5-6.0% of fixed carbon and 4-7% of gas volatile matters. The alkalinity of the covering slag, namely the ratio of CaO to SiO2, is 0.91 to 1.00, the melting point of the covering slag is 1100 DEG C to 1160 DEG C, and the viscosity of the covering slag is 0.3 to 0.6 Pa.s at 1300 DEG C. The invention can solve the problems of easy crusting, slag entrainment, slag inclusion, slag sticking on casting blank surfaces, bubbles under skins, cracks, deep chatter mark, felting, bleed-out, and the like of the covering slag in the crystallizer during high-manganese high-nitrogen low-nickel stainless steel plate blank continuous casting, and has the advantages of uniform and stable slagging in the crystallizer, good casting blank quality, difficult felting and bleed-out, and the like.
Description
Technical field
The invention belongs to the steelmaking ingredient technical field, be specifically related to a kind of high manganese and high nitrogen low nickel stainless steel sheet billet continuous casting crystallizer protecting residue and preparation method thereof.
Technical background
The high manganese and high nitrogen low nickel stainless steel is representative with steel grades such as AlSl201, AlSl202, Jindal J1, Jindal J3, Jindal J4, and its main feature is:
1), the nascent solidified shell amount of contraction of this type of steel grade is little.Because alloying element contents such as manganese, chromium are higher in such steel; therefore the nascent solidified shell of its strand is harder; the space is less between base shell and the crystallizer wall; the difficult inflow of covering slag melt cinder easily causes covering slag slag consumption introductory note to play the bonding steel leakage accident and slag film skewness, heat transfer inequality cause defectives such as crackle.
2), gas content height in the molten steel.Because such steel grade is to adopt manganese, the nitrogen low-cost stainless steel for nickel, in the steel gas particularly nitrogen content produce the rimhole defective than higher if covering slag designs the improper strand that very easily causes.
3), fluidity molten steel is poor, watering property is poor.Because the alloy of such molten steel own, gas content are higher; should not carry out measures such as argon blowing in the casting; therefore fluidity molten steel is relatively poor; be clamminess easily; temperature is lower at the interface to cause molten steel and covering slag melt cinder; covering slag is difficult for fusing, is prone to problems such as covering slag lumps in crystallizer, liquid slag layer thin, volume slag, bonding steel leakage.
In sum, because these characteristics of high manganese and high nitrogen low nickel stainless steel self cause being prone in the casting cycle problems such as crust, volume slag, slag inclusion, casting billet surface dry slag, rimhole, crackle, bonding steel leakage.
Before the present invention; the low nickel slab stainless steel protection residue product of high manganese and high nitrogen on the domestic market be that external covering slag producer monopolizes substantially; comprise that the domestic patent No. that is fit to such steel grade is 200810039376.8; 200410064582.6; 200710193114.2 covering slag the solution thinking of stainless steel slab continuous casting be may be summarized to be substantially be high basicity; low melting point; the low viscosity slag; promptly generally speaking with the design of the basicity of such covering slag more than 1.0; the fusing point design is below 1100 ℃; viscosity under 1300 ℃ is below 0.3Pa.S, and purpose is to solve such steel grade easily to crack; watering property is poor; easily bonding waits defect problem.Though this covering slag has comparatively significantly effect to solving defectives such as crackle, bonding steel leakage, because covering slag fusing point, viscosity are lower, cause its slag consumption higher, easily dry slag, volume slag cause the strand oscillation mark darker; In addition, the molten speed of such covering slag is very fast, heat insulating ability is poor, is prone to problems such as crust, strand rimhole, the increase of bonding steel leakage tendency.
Summary of the invention
At the problems referred to above; the purpose of this invention is to provide a kind of high manganese and high nitrogen low nickel stainless steel sheet billet continuous casting crystallizer protecting residue and preparation method thereof; high manganese and high nitrogen low nickel stainless steel slab continuous casting crystallizer protection slag of the present invention has adopted and has been different from the thinking that prior art is high basicity, low melting point, low viscosity, the pre-melt of use, but has adopted the new thought of low basicity, high-melting-point, high viscosity, the non-fritting base-material of use.
High manganese and high nitrogen low nickel stainless steel slab continuous casting crystallizer protection slag of the present invention, its composition of raw materials percentage by weight consists of: wollastonite 54～57%, fluorite 9～13%, sodium carbonate 9～13%, lithium carbonate 0～1%, glass dust 5～7%, aluminium vanadine 8～12%, carbon black 2.5～2.7%, graphite 3～3.5% are formed.
The covering slag that adopts above-mentioned raw materials to make; its chemical component weight percentage is: calcium oxide 31.9～34.9%, silica 32.1～35.1%, alundum (Al 7.3～8.3%, magnesia 0.5～1.5%, di-iron trioxide 0.5～1.4%, fluorine ion 4.4～6.4%, sodium oxide molybdena 6.5～7.5%, lithia 0～0.39%, fixed carbon 4.5～6.0%, gaseous volatilization thing 4～7%.
Described carbon black derive from the semi-reinforcing carbon black of domestic or import, wear-resisting carbon black, in the super carbon black one or more.
High manganese and high nitrogen low nickel stainless steel sheet billet continuous casting of the present invention is CaO/SiO with crystallizer protecting residue basicity
2Be 0.91～1.00,1100 ℃～1160 ℃ of fusing points, 1300 ℃ of following viscosity 0.3～0.6Pa.s.
The preparation method of high manganese and high nitrogen low nickel stainless steel slab continuous casting crystallizer protection slag of the present invention is characterized in that and raw material need not be made the fritting base-material in advance, to save manufacturing cost.This preparation method's step is as follows:
1) with described raw materials by weight percent (ore deposit) wollastonite, aluminium vanadine, graphite, fluorite fragmentation, levigate, its particle diameter is reached below 45 microns, make breeze; With described raw materials by weight percent glass slag fragmentation, levigate, its particle diameter is reached below 45 microns, make glass dust;
2), add water through sufficient mechanical mixing stirring and size mixing with after the mixing of the raw meal in the step 1); The sodium carbonate, the lithium carbonate that add described percentage by weight, the carbon black that dissolves the described percentage by weight of back adding stirs in advance, add percentage by weight then and be 1.5～2% binding agent and percentage by weight and be 0.1～0.3% water reducer, stir mist projection granulating behind the defibrination;
3) covering slag of drying and moulding is cooled in storage bin below 100 ℃ after the granulation, granularity requirements: 0～0.2mm, the wherein above particle diameter of 0.17mm more than 90%; Packing moisture content≤0.30%.
Binding agent of the present invention is sodium carboxymethylcellulose or starch; Described water reducer is a calcium lignosulfonate.
Mentality of designing and principle that the present invention is concrete are as follows:
1, basicity (CaO/SiO
2) design
Basicity is important index of covering slag, and it is determining the design system position of whole protecting slag.Covering slag is with CaO-SiO under regular situation
2-Al
2O
3Low melting point zone in the ternary phase system is designed, and its basicity is in 0.8～1.5 this zone.Along with the increase of covering slag basicity, its tendency towards devitrification increases, and it is separated out crystal grain and develops to thickization direction greater than 1.0 backs in basicity, and this is favourable to suppressing to conduct heat, solve crackle, but for lubricated be disadvantageous.
Find by practice, under covering slag fusing point and viscosity condition with higher, if adopt higher basicity; can cause covering slag greasy property variation so, the bonding steel leakage tendency increases a lot, Given this; the basicity design 0.91～1.00, there are enough greasy properties to guarantee covering slag.
2, Al
2O
3The design of content
Al
2O
3On chemical property, belong to amphoteric oxide, in the covering slag system, it is used as normally that an acidic oxide treats under the alkali condition, and it is used as normally that basic anhydride treat under acid condition.Al
2O
3Bigger to the influence of covering slag viscosity, crystallization tendency, along with the increase of its content, the viscosity of covering slag, crystallization tendency increase.At the characteristic of high manganese and high nitrogen low nickel stainless steel, adopt higher viscosity will help controlling the depth of chatter mark of casting billet surface, help obtaining the strand of great surface quality, therefore with high manganese and high nitrogen low nickel stainless steel covering slag Al
2O
3Content is determined between 7.3%～8.3%.
3, the design of fusing point
Generally, from solving the angle of crackle, fusing point is high more, is not easy more to crack, because the fusing point height after in the crystallizer initial solidification shell increase even index increase that the covering slag thermal resistance increases, covering slag conducts heat with solid slag film thickness between the crystallizer copper wooden partition; Therefore high more being not easy more of fusing point cracks, but considers that high manganese and high nitrogen low nickel stainless steel liquidus temperature is lower, melting condition is abominable, and fusing point can only be higher slightly than GPF (General Protection False slag, and fusing point is determined 1100 ℃～1160 ℃ these scopes.
4, the design of viscosity
Because high manganese and high nitrogen low nickel stainless steel initial solidification shell is harder; base shell and crystallizer wall paste tightlyer; melt cinder is difficult for flowing between initial solidification shell and the crystallizer wall; the consumption of covering slag will reduce relatively; in order to increase the slag consumption, to reduce the risk of bonding steel leakage, should design viscosity smaller usually, but covering slag viscosity little after; can cause covering slag slag consumption to increase, the strand oscillation mark deepens.Practice is found, 1300 ℃ of following viscosity of high manganese and high nitrogen low nickel stainless steel covering slag are controlled at this scope of 0.3～0.6Pa.s, can not produce bleed-out and oscillation mark shoals, and has improved slab quality.
The design of 6, joining carbon
The principle that high manganese and high nitrogen low nickel stainless steel covering slag is joined carbon is that the supply of molten speed assurance melt cinder will be got well, can effectively be controlled to heat insulation effect.High insulating effect avoids covering slag to crust in crystallizer, avoid being clamminess; High insulating effect, the molten steel surface temperature is higher, and the meniscus place can premature solidification, helps the effusion of gas in the molten steel, thereby avoids the generation of rimhole.Therefore high manganese and high nitrogen low nickel stainless steel covering slag is joined the compound carbon pattern of joining that carbon has adopted higher carbon content (fixed carbon content 4.5%～6.0%) and " carbon black+graphite "; its pair material is joined the carbon type order is to make covering slag not only at slag layer but also when sinter layer has preferably insulation effect; make it that comparatively clearly demarcated slag layer, sinter layer, liquid slag layer structure are arranged in crystallizer again, guarantee the supply of melt cinder.
7, the design of batching system
High manganese and high nitrogen low nickel stainless steel covering slag of the present invention need not be made the fritting base-material in advance with raw material, and the various raw materials that directly will meet the chemical composition mass percent stir the back mist projection granulating by the percentage by weight mixing defibrination of its batching and make.Because do not contain more gaseous volatilization thing through in the raw material of fritting; after covering slag adds crystallizer; these gases at first decomposes are overflowed; make the covering slag particle on microcosmic, present loose porous state; the heat of molten steel can evenly disperse in these holes; make the covering slag thermally equivalent; thereby reach the purpose that covering slag is stablized slagging, stable consumptions, avoid the pre-melted type covering slag on the high manganese and high nitrogen low nickel stainless steel owing to the easy caking that the gas permeability difference occurs, melt phenomenons such as inhomogeneous.
High manganese and high nitrogen low nickel stainless steel slab continuous casting crystallizer protection slag of the present invention; can effectively solve the covering slag that occurs in the present high manganese and high nitrogen low nickel stainless steel sheet billet continuous casting and in crystallizer, easily crust, roll up problems such as slag, slag inclusion, casting billet surface dry slag, rimhole, crackle, oscillation mark are dark, bonding steel leakage, have that crystallizer internalization slag is uniform and stable, slab quality good, be difficult for advantage such as bonding steel leakage.
The specific embodiment
Below by embodiment the present invention is described further.
Embodiment 1
The high manganese and high nitrogen low nickel stainless steel sheet billet continuous casting covering slag that present embodiment provides, see list of ingredients 1:
Steel mill's continuous casting process: casting section 200*1250mm
2, pulling rate 0.8～1.2m/min, molten steel chemical composition (percentage by weight): C:0.11%, Si:0.43%, Mn:10.20%, P:0.055%, S::0.005%, Cr:13.20%, Ni:0.75%, Cu:1.56%, N:0.25%.
Open when watering starting; covering slag of the present invention is evenly pushed crystallizer, require evenly to cover whole molten steel face, the total slag blanket of covering slag (being slag layer, sinter layer, liquid slag layer threeply degree sum) is between 20～45mm; keep black slag operation, must not make the molten steel face exposed.
Open water after, the molten steel ground roll moves in 3mm, pulling rate is stabilized in 1.1m/min, this moment measure about liquid slag layer thickness 9mm.After this survey a liquid slag layer every 20min, its thickness is at 8～12mm.In casting cycle, the crust clustering phenomena is sprawled well, do not had to this covering slag in crystallizer, flare is moderate, the change slag is uniform and stable; Slag bar rule and less need not chosen the slag bar generally speaking, and by statistics, this covering slag slag consumption is about 0.3Kg/ ton steel.
Observe strand under the cold conditions, oscillation mark is clear, regular, more shallow, does not have and is stained with slag, volume slag phenomenon, and casting billet surface overall flat lay the grain is sliding no abnormal, and reconditioning quality descends more than 90%, and strand primes qualification rate is more than 99.9%.
Strand hot rolled coil quality with covering slag of the present invention uses the qualification rate of original covering slag to be greatly improved than steel mill, and hot rolled coil primes qualification rate has been brought up to more than 99% by original 81.2%.
Embodiment 2
The high manganese and high nitrogen low nickel stainless steel sheet billet continuous casting covering slag that present embodiment provides, see list of ingredients 2:
Steel mill's continuous casting process: casting section 210*1200mm
2, pulling rate 0.75～1.0m/min, molten steel chemical composition (percentage by weight): C:0.12%, Si:0.48%, Mn:10.11%, P:0.047%, S::0.004%, Cr:13.01%, Ni:0.79%, Cu:1.66%, N:0.27%.
Open when watering starting; covering slag of the present invention is evenly pushed crystallizer, require evenly to cover whole molten steel face, the total slag blanket of covering slag (being slag layer, sinter layer, liquid slag layer threeply degree sum) is between 20～45mm; keep black slag operation, must not make the molten steel face exposed.
Open water after, the molten steel ground roll moves in 3mm, pulling rate is stabilized in 0.95m/min, this moment measure about liquid slag layer thickness 9mm.After this survey a liquid slag layer every 20min, its thickness is at 8～12mm.In casting cycle, the crust clustering phenomena is sprawled well, do not had to this covering slag in crystallizer, flare is moderate, the change slag is uniform and stable; The slag status is good, need not choose the slag bar when pouring technology is stablized.By statistics, this covering slag slag consumption is about the steel of 0.32Kg/ village.
Observe strand under the cold conditions, oscillation mark is clear, regular, more shallow, does not have and is stained with slag, volume slag phenomenon, and casting billet surface overall flat lay the grain is sliding no abnormal, and strand primes qualification rate is more than 99.9%.
Strand hot rolled coil quality with covering slag of the present invention uses the qualification rate of original covering slag to be greatly improved than steel mill, and hot rolled coil primes qualification rate has been brought up to more than 99% by original 89%.
Embodiment 3
The high manganese and high nitrogen low nickel stainless steel sheet billet continuous casting covering slag that present embodiment provides, see list of ingredients 3:
Steel mill's continuous casting process: casting section 200*1260mm
2, pulling rate 0.9～1.3m/min, molten steel chemical composition (percentage by weight): C:0.11%, Si:0.51%, Mn:10.17%, P:0.05%, S::0.005%, Cr:13.16%, Ni:0.83%, Cu:1.68%, N:0.29%.
Open when watering starting; covering slag of the present invention is evenly pushed crystallizer, require evenly to cover whole molten steel face, the total slag blanket of covering slag (being slag layer, sinter layer, liquid slag layer threeply degree sum) is between 20～45mm; keep black slag operation, must not make the molten steel face exposed.
Open water after, the molten steel ground roll moves in 3mm, pulling rate is stabilized in 1.2m/min, this moment measure about liquid slag layer thickness 10mm.After this survey a liquid slag layer every 20min, its thickness is at 8～12mm.In casting cycle, the crust clustering phenomena is sprawled well, do not had to this covering slag in crystallizer, flare is moderate, the change slag is uniform and stable; The slag status is good, need not choose the slag bar when pouring technology is stablized.By statistics, this covering slag slag consumption is about 0.31Kg/ ton steel.Observe strand under the cold conditions, oscillation mark is clear, regular, more shallow, does not have and is stained with slag, volume slag phenomenon, and casting billet surface overall flat lay the grain is sliding no abnormal, and strand primes qualification rate is more than 99.9%.
Strand hot rolled coil quality with covering slag of the present invention uses the qualification rate of original covering slag to be greatly improved than steel mill, and hot rolled coil primes qualification rate has been brought up to more than 99% by original 86%.
Claims (6)
1. high manganese and high nitrogen low nickel stainless steel slab continuous casting crystallizer protection slag, percentage by weight consists of: wollastonite 54～57%, fluorite 9～13%, sodium carbonate 9～13%, lithium carbonate 0～1%, glass dust 5～7%, aluminium vanadine 8～12%, carbon black 2.5～2.7%, graphite 3～3.5% are formed.
2. high manganese and high nitrogen low nickel stainless steel slab continuous casting crystallizer protection slag according to claim 1; it is characterized in that described high manganese and high nitrogen low nickel stainless steel slab continuous casting crystallizer protection slag adopts above-mentioned raw materials to make; its chemical component weight percentage is: calcium oxide 31.9～34.9%, silica 32.1～35.1%; alundum (Al 7.3～8.3%; magnesia 0.5～1.5%; di-iron trioxide 0.5～1.4%; fluorine ion 4.4～6.4%; sodium oxide molybdena 6.5～7.5%; lithia 0～0.39%; fixed carbon 4.5～6.0%; gaseous volatilization thing 4～7%.
3. high manganese and high nitrogen low nickel stainless steel slab continuous casting crystallizer protection slag according to claim 1, it is characterized in that described carbon black be semi-reinforcing carbon black, wear-resisting carbon black, in the super carbon black one or more.
4. according to claim 2 or 3 described high manganese and high nitrogen low nickel stainless steel slab continuous casting crystallizer protection slags, it is characterized in that the basicity of described high manganese and high nitrogen low nickel stainless steel slab continuous casting crystallizer protection slag is CaO/SiO
2: 0.91～1.00,1100 ℃～1160 ℃ of fusing points, the viscosity 0.3Pa.S～0.6Pa.S under 1300 ℃.
5. preparation method of high manganese and high nitrogen low nickel stainless steel slab continuous casting crystallizer protection slag according to claim 1 is characterized in that and raw material need not be made the fritting base-material in advance that this preparation method's step is as follows:
1) with described raw materials by weight percent wollastonite, aluminium vanadine, graphite, fluorite fragmentation, levigate, its particle diameter is reached below 45 microns, make breeze; With described raw materials by weight percent glass slag fragmentation, levigate, its particle diameter is reached below 45 microns, make glass dust;
2), add water through sufficient mechanical mixing stirring and size mixing with after the mixing of the raw meal in the step 1); The sodium carbonate, the lithium carbonate that add described percentage by weight, the carbon black that dissolves the described percentage by weight of back adding stirs in advance, add percentage by weight then and be 1.5～2% binding agent and percentage by weight and be 0.1～0.3% water reducer, stir mist projection granulating behind the defibrination;
3) covering slag of drying and moulding is cooled in storage bin below 100 ℃ after the granulation, granularity requirements: 0～0.2mm, the wherein above particle diameter of 0.17mm more than 90%; Packing moisture content≤0.30%.
6. according to the preparation method of the described high manganese and high nitrogen low nickel stainless steel of claim 5 slab continuous casting crystallizer protection slag, it is characterized in that described binding agent is sodium carboxymethylcellulose or starch; Described water reducer is a calcium lignosulfonate.
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