CN101956131B - Preparation method of ultra-low carbon steel and ultra-low carbon steel plate - Google Patents
Preparation method of ultra-low carbon steel and ultra-low carbon steel plate Download PDFInfo
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- CN101956131B CN101956131B CN2009101501745A CN200910150174A CN101956131B CN 101956131 B CN101956131 B CN 101956131B CN 2009101501745 A CN2009101501745 A CN 2009101501745A CN 200910150174 A CN200910150174 A CN 200910150174A CN 101956131 B CN101956131 B CN 101956131B
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Abstract
The invention provides a preparation method of ultra-low carbon steel, comprising the following steps: carrying out pre-deoxidation and alloying, desulfuration, thermoregulation, decarburization and alloy fine adjustment on molten steel; before thermoregulation of the molten steel, adding a slag-adjusting agent containing A1 which accounts for 8-12% of the total weight of the slag-adjusting agent to the surface of ladle slag so that the content of (FeO+MnO) in the ladle slag is not more than 20wt% of the total weight of the ladle slag; after decarburization and alloy fine adjustment, circulating the molten steel under a vacuum condition so that the content of T[O] in the steel is 0.0025-0.004wt% of the total weight of the steel; continuously injecting the obtained molten steel into a crystallizer, and adding casting powder; and continuously drawing out the molten steel with a hard shell from the outlet of the crystallizer to obtain a continuous casting billet. In the method, the viscosity of the casting powder at 1300 DEG C is 0.2-0.3Pa.S, alkalinity is 0.8-1.1, and melting point is 1040-1130 DEG C; the broad-face heat flux density and the narrow-face heat flux density of the cooling crystallizer are 1350-1416kw/sq.m. and 1122-1174kw/sq.m. respectively, and the heat flux ratio of the broad face to the narrow face of the crystallizer is 0.8-0.85; and continuous casting speed is 0.8-1.3m/min.
Description
Technical field
The present invention relates to a kind of preparation method of ultra low-carbon steel and the preparation method of ultra low-carbon steel sheet material.
Background technology
The Ultra-low carbon deep drawing steel is mainly used in production auto sheet, tame electroplax etc. to the strict cold-rolling galvanization plate of surperficial specification of quality, because such sheet metal thickness is thinner, is generally the 0.8-1.6 millimeter; Rolling compression ratio reaches more than 120; Therefore, if in the strand to be mingled with content higher or to be mingled with size bigger, after excessive compression ratio is rolling; The cold-reduced sheet surface is mingled with streak shape defective with occurring, and influences quality product.The Ultra-low carbon deep drawing steel generally contains a certain amount of microalloy element in addition, like Al, V, Ti etc., in continuous casting production process; Because of being at austenite grain boundary with AlN, TiN, V forms such as (CN) when temperature reduces, the Al of solid solution under the high temperature, V, Ti dynamically separate out or static state is separated out; Further increased crack sensitivity, when the casting machine strand was aligned, inner arc received tension stress; Because the notch effect of oscillation mark produces stress concentration, has quickened the formation and the expansion of crackle.Therefore, casting billet surface is prone to produce tiny crack when adopting continuous casting production to contain the ultra low-carbon steel of Al, V, Ti, and the strand that contains tiny crack also possibly produce streak shape defective through after rolling on cold-reduced sheet.Therefore; Adopt rational refining continuous casting process; Improve the molten steel cleanliness factor; Reduce molten steel and be mingled with content, improving casting billet surface and subcutaneous quality is the key link of production high-quality ultra low-carbon steel, and research and development are the core technologies that alleviates and eliminate ultra low-carbon steel strip defective with the refining continuous casting process that ultra low-carbon steel adapts.
" iron and steel " magazine in November, 2005 (the 40th volume the 12nd phase 28-30 page or leaf reduces the production practice of cold-rolled IF steels surface inclusion, works such as Meng Jingsong) has been reported the cold-rolled IF steels production practice in a few years of Anshan iron and steel plant warp.Anshan iron and steel plant through further transformation, improve production unit and system optimization, require to supply with carbon content≤500 * 10 in the crude steel liquid of RH refining treatment
-6, oxygen level≤(400-600) * 10
-6, tundish adopts the flow control device of turbulence inhibitor, uses to absorb Al
2O
3Tundish covering flux that the ability that is mingled with is strong and crystallizer protecting residue; Optimize the geometric parameter and the casting parameters of mold submerged nozzle; Promote inclusion floating and prevent that molten steel from measures such as volume slag taking place, IF steel cold-reduced sheet is mingled with scrap rate and is reduced to 0.61% by 10.37% before tackling key problems.
" steel research " magazine in September, 2006, (the 34th volume the 5th phase 55-57 page or leaf reduced the technical study of IF steel w (O), Wang Xiongzhu) has reported the production practice of Wuhan Iron and Steel Plant control IF steel cleanness.Wuhan Iron and Steel Plant adopts converter smelting dynamically to control in steelmaking process; Improve two hit rates, top bottom compound blowing technology, tapping pushing off the slag, ladle slag upgrading of converter w (C) and temperature, the ladle temperature that assurance is enough; Avoid RH to adopt the intensification means, guarantee behind the deoxidation alloying that molten steel cycling time is greater than waiting measure in 7 minutes; In casting process, adopt continuous casting protection cast, tundish adopt slag basic, the automatic control stabilization precision of mold liquid level at ± 3mm, adopt measures such as full-bodied crystallizer protecting residue, use large vol tundish, make IF steel w (O) by average 34.1 * 10 of the past
-6Drop to average 17.6 * 10
-6(fluctuation range 12 * 10
-6-24 * 10
-6), one that has realized the molten steel purity than quantum leap.
But aforesaid method can't solve for strand in continuous casting of ultralow carbon steel production and occur map cracking and transverse crack easily, makes that the cracking frequency of strand is higher, and can cause the problem that is occurred trace shape defective by the rolling sheet material that obtains of ultra low-carbon steel strand.
Summary of the invention
The objective of the invention is to overcome the ultra low-carbon steel strand that adopts existing method production to obtain and be prone to map cracking and transverse crack; Make the higher defective of cracking frequency of strand; And can cause the cold-rolling galvanization lath problem of trace shape defective to occur, the preparation method of lower ultra low-carbon steel of a kind of strand cracking frequency and ultra low-carbon steel sheet material is provided.
Contriver of the present invention finds; In above-mentioned research, solving the measure of IF steel bar trace shape defective major technique mainly is to improve the molten steel cleanliness factor; And for containing strand map cracking and the transverse crack defective that precipitates such as another main difficult technical AlN of running in aluminium, the production of titaniferous ultra low-carbon steel steel continuous casting, TiN bring out in the austenite grain boundary deposition; The cold-reduced sheet streak shape defective that causes, the present report of not seeing the specific aim measure as yet.
Improve the technical measures aspect that the molten steel cleanliness factor prevents to roll up slag in the above-mentioned in addition research, pulling rate control is not combined with using high-viscosity covering slag, molten steel in mold cleanliness factor control effect is not too obvious.
The invention provides a kind of preparation method of ultra low-carbon steel, this method comprises:
(1) molten steel that smelting is obtained carries out external refining, and the method for said external refining comprises carries out preliminary dexidation alloying and desulfurization with molten steel, makes that the activity oxygen level is that 0.04-0.06 weight %, S content are 0.006-0.015% weight % in the molten steel; And molten steel carried out temperature adjustment processing, decarburization and alloy fine setting, and making the gross weight with molten steel is benchmark, to be respectively C content be 0.003-0.005 weight % to each substances content in the molten steel; Si content is 0.002-0.03 weight %, and Mn content is 0.10-0.25 weight %, and P content is 0.006-0.015 weight %; S content is 0.006-0.015 weight %; Ti content is 0.050-0.085 weight %, and Als content is 0.02-0.08 weight %, and surplus is an iron;
(2) molten steel after the external refining is carried out continuous casting, the method for said continuous casting comprises the molten steel after the external refining is injected in the mold continuously, and in mold, adds covering slag; Cooling crystallizer makes the molten steel surface duricrust that congeals into, and the outlet of this molten steel with duricrust from mold pulled straight, and makes it in secondary cooling zone and the cooling of straightening district and all solidify, and the outlet in the straightening district obtains continuously cast bloom;
Wherein, In step (1), molten steel is carried out after preliminary dexidation alloying and the desulfurization, before temperature adjustment handles, adds the slag supplying agent that Al content accounts for slag supplying agent gross weight 8-12% at the ladle slag top of the slag; Make in the ladle slag based on the ladle slag gross weight, (FeO+MnO) content is≤20 weight %; And after decarburization and alloy fine setting, molten steel is circulated under vacuum condition, the feasible gross weight with steel of the condition of vacuum cycle is a benchmark, T in the steel [O] content is 0.0025-0.004 weight %;
In step (2), the viscosity of said covering slag in the time of 1300 ℃ is 0.2-0.3PaS, and basicity is 0.8-1.1, and fusing point is 1040-1130 ℃; It is 1350-1416 kilowatt/square metre that cooling crystallizer makes the heat flow density of wide of mold, and the heat flow density of leptoprosopy is 1122-1174 kilowatt/square metre, and mold leptoprosopy and wide heat flow density are than being 0.8-0.85; The pulling rate that the said molten steel that will have a duricrust pulls straight from the outlet of mold be 0.8-1.3 rice/minute.
The present invention also provides a kind of preparation method of ultra low-carbon steel sheet material, and this method comprises rolling ultra low-carbon steel strand, and wherein, said ultra low-carbon steel strand is for to be made by method of the present invention.
Adopt method of the present invention can improve the ultra low-carbon steel steel quality, eliminate ultra low-carbon steel casting billet surface tiny crack defective, thereby eliminate because of being mingled with the ultra low-carbon steel galvanized sheet strip defective that causes with the casting billet surface tiny crack.This method not only is specially adapted to the strong steel alloy that contains aluminium, vanadium or titanium of continuous casting crackle susceptibility, is applicable to that too strict and strand produces the steel grade that is prone to produce crizzle to steel for other deep drawing steel, high-grade pipe line steel etc.
Embodiment
According to the present invention, the preparation method of said ultra low-carbon steel comprises:
(1) molten steel that smelting is obtained carries out external refining, and the method for said external refining comprises carries out preliminary dexidation alloying and desulfurization with molten steel, makes that the activity oxygen level is that 0.04-0.06 weight %, S content are 0.06-0.015 weight % in the molten steel; And molten steel carried out temperature adjustment processing, decarburization and alloy fine setting, and making the gross weight with molten steel is benchmark, to be respectively C content be 0.003-0.005 weight % to each substances content in the molten steel; Si content is 0.002-0.03 weight %, and Mn content is 0.10-0.25 weight %, and P content is 0.006-0.015 weight %; S content is 0.006-0.015 weight %; Ti content is 0.050-0.085 weight %, and Als content is 0.02-0.08 weight %, and surplus is an iron;
(2) molten steel after the external refining is carried out continuous casting, the method for said continuous casting comprises the molten steel after the external refining is injected in the mold continuously, and in mold, adds covering slag; Cooling crystallizer makes the molten steel surface duricrust that congeals into, and the outlet of this molten steel with duricrust from mold pulled straight, and makes it in secondary cooling zone and the cooling of straightening district and all solidify, and the outlet in the straightening district obtains continuously cast bloom;
Wherein, In step (1), molten steel is carried out after preliminary dexidation alloying and the desulfurization, before temperature adjustment handles, adds the slag supplying agent that Al content accounts for slag supplying agent gross weight 8-12% at the ladle slag top of the slag; Make in the ladle slag based on the ladle slag gross weight, (FeO+MnO) content is≤20 weight %; And after decarburization and alloy fine setting, molten steel is circulated under vacuum condition, the feasible gross weight with steel of the condition of vacuum cycle is a benchmark, T in the steel [O] content is 0.0025-0.004 weight %;
In step (2), the viscosity of said covering slag in the time of 1300 ℃ is 0.2-0.3PaS, and basicity is 0.8-1.1, and fusing point is 1040-1130 ℃; It is 1350-1416 kilowatt/square metre that cooling crystallizer makes the heat flow density of wide of mold, and the heat flow density of leptoprosopy is 1122-1174 kilowatt/square metre, and mold leptoprosopy and wide heat flow density are than being 0.8-0.85; The pulling rate that the said molten steel that will have a duricrust pulls straight from the outlet of mold be 0.8-1.3 rice/minute.
According to the present invention; Method provided by the invention mainly is through the ladle slag modification, increases the step of molten steel circular treatment under vacuum condition, the integrated use that improves technical measures such as covering slag viscometric properties in the continuous cast mold, reduction casting machine pulling rate and the steel quality that synergy improves ultra low-carbon steel; Thereby eliminate the defective that the ultra low-carbon steel casting billet surface is prone to tiny crack, and eliminate because of being mingled with the problem that there is the strip defective in the ultra low-carbon steel sheet material that causes with the casting billet surface tiny crack.
Wherein, said activity oxygen level refers to free oxygen concn in the molten steel, and said activity Determination of Oxygen method is conventionally known to one of skill in the art, for example: adopt apparatus for determination of oxygen to measure; Said T [O] (total oxygen content) comprises in the molten steel oxygen level in the activity oxygen level and inclusion; The measuring method of T in the said steel [O] is conventionally known to one of skill in the art, for example: adopt the TC600 oxygen-nitrogen analyzer to measure.
According to the present invention; After molten steel is carried out preliminary dexidation alloying and desulfurization, before temperature adjustment handles; Add the slag supplying agent that Al content accounts for slag supplying agent gross weight 8-12% at the ladle slag top of the slag, make in the ladle slag that based on the ladle slag gross weight, (FeO+MnO) content is≤20 weight %; Be preferably 5-18.5 weight %; Add the reductibility slag supplying agent total content of (FeO+MnO) in the ladle slag is reduced, can guarantee that the oxidisability inclusion in the molten steel floats in the ladle slag on further, thereby improve the quality of molten steel.Wherein, can be variously can reach the slag supplying agents that reduce the total content of FeO+MnO in the ladle slag in the kind of the slag supplying agent that the ladle slag top of the slag adds, under the preferable case, said slag supplying agent can contain CaO, SiO
2, Al
2O
3, MgO and Al, be benchmark with the gross weight of this slag supplying agent, the content of said CaO is 40-50 weight %, said SiO
2Content be 4-6 weight %, said Al
2O
3Content be 35-45 weight %, the content of said MgO is 2-4 weight %, the content of said Al is 8-12 weight %; As long as the consumption of said slag supplying agent can guarantee the total content of (FeO+MnO) in the ladle slag and reduce to≤20 weight % that under the preferable case, molten steel per ton can add 4-6 kilogram slag supplying agent.
According to the present invention, in the said ladle slag in the measuring method of FeO and the ladle slag measuring method of MnO be conventionally known to one of skill in the art: for example, can adopt dichromate titration (chemical assay) to measure the content of FeO in the ladle slag; Can adopt infrared spectrometry (determining instrument employing x-ray spectrometer) is the content that fluorescent method (physical measurement) is measured MnO in the ladle slag.
According to the present invention, after decarburization and alloy fine setting, the feasible gross weight with molten steel of the condition of vacuum cycle is a benchmark, and T in the steel [O] content is 0.0025-0.0040 weight %, helps effectively to improve the molten steel cleanliness factor.Molten steel is preferably carried out in the RH vacuum unit in the circulation under the vacuum condition, and the pressure in the said RH vacuum unit is the 50-100 handkerchief; Argon gas be blown into intensity be molten steel 8-12 liter per ton/minute, the vacuum cycle time can be 5-7 minute.According to the present invention, said molten steel weight is the 120-140 ton hour, the flow of argon gas can for the 1200-1500 liter/minute, the vacuum cycle time can be 5-7 minute.
According to the present invention, making the viscosity of said covering slag in the time of 1300 ℃ is 0.2-0.3PaS, and (said basicity refers to CaO and SiO in the covering slag to basicity
2Weight ratio) be 0.8-1.1, fusing point is 1040-1130 ℃, helps to prevent the molten steel volume slag of casting process and improve covering slag to absorb the ability that is mingled with.Said covering slag can be the conventional various covering slags in this area; As long as can make viscosity, basicity and the fusing point of said covering slag in the time of 1300 ℃ reach requirement of the present invention; For example, can reach the purpose of control covering slag viscosity, basicity and fusing point through the method for each component and content in the adjusting covering slag.
According to the present invention, said covering slag contains CaO, SiO
2, Al
2O
3, Na
2O, CaF
2And C, be benchmark with the gross weight of this covering slag, the content of said CaO is 25-40 weight %, said SiO
2Content be 28-40 weight %, said Al
2O
3Content be 2-6 weight %, said Na
2The content of O is 6-10 weight %, said CaF
2Content be 3-10 weight %, the content of said C is 2-10 weight %.The adjustable extent broad of the consumption of said covering slag adopts covering slag according to the invention can also reduce its consumption, increases the thickness of liquid slag layer (being the liquid state protection slag blanket between solid-state protection slag blanket and the liquid steel level), to play the better protection effect.For example, the consumption of said covering slag can be reduced to 0.45-0.55 kg/ton steel by 0.60-0.75 kg/ton steel, and the liquid slag layer gauge control can be brought up to the 10-12 millimeter by the 7-9 millimeter.
The preparation method of said covering slag is conventionally known to one of skill in the art, for example, can be pre-melted slag or mechanically mixing slag, and wherein: CaO can derive from the material that pre-melted slag, wollastonite, cement clinker etc. contain CaO; SiO
2Can derive from pre-melted slag, wollastonite, cement clinker, silica sand, feldspar etc. and contain SiO
2Material; Al
2O
3Can derive from pre-melted slag, bauxitic clay, cement clinker, white clay etc. and contain Al
2O
3Material; Na
2O can derive from pre-melted slag, Na
2CO
3Deng containing Na
2The material of O; F
-Can derive from pre-melted slag, CaF
2(fluorite) etc. contains F
-Material, C can derive from the material that carbon black, graphite and coke etc. contain C.
According to the present invention; Wide of mold and leptoprosopy heat flow density can be controlled at 1350-1416 kilowatt/square metre and 1122-1174 kilowatt/square metre respectively; Mold leptoprosopy and wide 's heat flow density ratio is 0.80-0.85; Can make the interior strand cooling of mold evenly, nascent solidified shell is evenly grown.In the present invention, wide heat flow density of said mold is meant the heat that the unit surface water coolant of wide of mold is taken away, and the leptoprosopy heat flow density is meant the heat that the unit surface water coolant of mold leptoprosopy is taken away; Said heat flow density ratio is the ratio of leptoprosopy heat flow density and wide heat flow density.
According to the present invention, the method for said cooling crystallizer can be for 20-40 ℃ water quench mold, and can calculate the heat flow density of wide/leptoprosopy of mold according to the following equation:
Wide/leptoprosopy cooling water flow on wide/leptoprosopy heat flow density=unit surface (rise/minute square metre) * cooling range (℃) * specific heat of water holds (4.183kJ/ (L ℃))/60 (s/min)
Wherein, The water coolant and the temperature head that goes out the water coolant of mold of mold gone in the temperature difference fingering of said water coolant; The temperature difference of said water coolant is relevant with the speed of pulling rate, and the flow of water coolant and the temperature difference of water coolant all can online in real time be measured the copper plate of crystallizer area; Be that mold single face (wide/leptoprosopy) area also can be measured when mold reached the standard grade use, measuring method is conventionally known to one of skill in the art.
Under the preferable case; On the unit surface; Wide cooling water inflow of mold can for the 1540-4115 liter/minute square metre, the leptoprosopy cooling water inflow of mold can be under the situation of 1385-3889 liter/minute square metre more preferably, on the unit surface; Wide cooling water inflow of mold can for the 2920-2942 liter/minute square metre, the leptoprosopy cooling water inflow of mold can for the 2050-2170 liter/minute square metre.
According to the present invention, the pulling rate that said molten steel with duricrust is pulled straight from the outlet of mold is controlled to be 0.8-1.3 rice/minute can effectively reduce the level fluctuation in the casting process mold, thus steel quality in the crystallization control device.
According to the present invention, the condition of said smelting molten steel and method can be for well known to a person skilled in the art the whole bag of tricks, for example, and the method for bessemerizing.
According to the present invention, in the said external refining molten steel is carried out deoxidation alloying and in advance desulfurization, and also can adopt the method for this area routine to carry out the method that molten steel carries out further desulfurization and decarburization and alloy fine setting.
Wherein, under the preferable case, the method for said preparatory desulfurization comprises that (said basicity refers to CaO and SiO in the refining slag with basicity
2Weight ratio) be that the refining slag of 80-100 mixes with molten steel, the consumption of said refining slag is a 4-6 kg/ton steel.Said refining slag generally contains quickened lime and fluorite, is benchmark with the total amount of refining slag, and the content of said quickened lime can be 70-85 weight %, and the content of said fluorite can be 15-30 weight %.
Said fluorite can be the fluorite of the various routines of this area use, and for example: the staple in the said fluorite is CaF
2, wherein, CaF
2Content be generally 70-90 weight %, SiO
2: 10-30 weight %, S :≤0.10 weight %, P :≤0.06 weight %, moisture content is less than 0.1 weight %;
Said quickened lime can be the quickened lime of the various routines of this area use, and the staple of said quickened lime is CaO, and wherein, the content of CaO is generally 80-90 weight %, and moisture content is less than 0.1 weight %.
The weave construction of lime and calcining temperature and calcination time are closely related, and therefore, the weave construction that influences activity of lime comprises the grain-size of volume density, void content, specific surface area and CaO mineral.Crystal grain is more little, and specific surface area is big more, and void content is high more, and lime is active just high more, and the chemical reaction ability is just strong more.The activity degree of said quickened lime is for characterizing an index of unslaked lime aquation speed of response, that is, with in the Ca (OH) that produces during with quicklime slaking
2The milliliter numerical table of the 4 mol hydrochloric acid that consumed shows.Generally, the activity degree of said quickened lime can be preferably the 300-500 milliliter for greater than 280 milliliters.
According to the present invention; Said temperature adjustment is handled and generally is meant being adjusted to certain temperature through the molten steel after preliminary dexidation alloying and the desulfurization, carries out next step processing then, according to the difference of treatment process; It is also different (according to the present invention that needed temperature is handled in temperature adjustment; Said temperature adjustment treatment temperature can be 1620-1635 ℃), said temperature adjustment is handled and generally in the LF stove, is carried out, and the step of said decarburization and alloy fine setting is preferably carried out in the RH vacuum unit.Said condition and the method for handling in temperature adjustment and in the RH vacuum unit, carry out decarburization and condition and method that alloy is finely tuned are conventionally known to one of skill in the art.
According to the present invention; After said molten steel with duricrust pulled straight from the outlet of mold; It is all solidified with the mobile water quench at secondary cooling zone and straightening district; Outlet in the straightening district obtains the method for continuously cast bloom also can be carried out according to the whole bag of tricks well known in the art, here repeats no more.
Need to prove; Method of the present invention can be used for various ultra low-carbon steels and contain aluminium, contain vanadium, micro-alloyed steel such as titaniferous; For example: Wheel Steel, pipe line steel etc.; Owing to the crack sensitivity of the steel alloy that contains aluminium, vanadium or titanium is strong, uses conventional method can't reach the purpose that reduces its cracking frequency, thereby especially be suitable for method of the present invention.For example, be benchmark with the gross weight of molten steel, C content is 0.0030-0.0050 weight % in the said ultra low-carbon steel; Si content is 0.002-0.03 weight %, and Mn content is 0.10-0.25 weight %, and P content is 0.006-0.015 weight %; S content is 0.006-0.015 weight %; Ti content is 0.050-0.085 weight %, and Als is 0.02-0.08 weight %, and surplus is an iron.
The present invention also provides a kind of preparation method of ultra low-carbon steel sheet material, and this method comprises rolling ultra low-carbon steel strand, and wherein, said ultra-low carbon steel slab is for to be made by method provided by the invention.
Wherein, the method for said rolling ultra low-carbon steel strand and condition are conventionally known to one of skill in the art, for example, and said rolling hot rolling and the cold-rolled process of comprising.The main flow process of said hot-rolled process is: strand is inserted in the process furnace; The strand temperature is brought up to 1050 ℃-1250 ℃, then strand is got into the breaking down unit, the strand of 200 millimeters thickness is rolled into the hot-rolled sheet of 30-40 millimeter thickness; Getting into crimper then makes the hot-rolled sheet temperature even; And then the entering finishing train, the hot-rolled sheet of 30-40 millimeter thickness is rolled into the hot-rolled sheet finished product of 2.5-10 mm thick, and curls into the hot-rolled sheet coil finished product.The main flow process of cold rolling operation is: the hot-rolled sheet coil finished product is at first carried out the uncoiling pickling remove impurity such as coiled sheet iron scale, get into tandem mills then, hot-rolled sheet coil thickness is rolled into the 0.5-2.0 mm thick, form cold-rolled products at last.
Below, will be described in more detail the present invention through embodiment.
High basicity refining slag used among the following embodiment contains quickened lime and fluorite, is benchmark with the total amount of refining slag, and the content of said quickened lime is 80 weight % (300 milliliters of activity degrees), and the content of said fluorite is 20 weight %.
Said reductibility slag supplying agent contains CaO, SiO
2, Al
2O
3, MgO and Al, in embodiment 1, be benchmark with the gross weight of slag supplying agent, the content of CaO is 45 weight %, said SiO
2Content be 6 weight %, said Al
2O
3Content be 35 weight %, the content of said MgO is 4 weight %, Al content 10 weight %; In embodiment 2, be benchmark with the gross weight of slag supplying agent, the content of CaO is 45 weight %, said SiO
2Content be 5 weight %, said Al
2O
3Content be 36 weight %, the content of said MgO is 2.5 weight %, Al content 11.5 weight %; In embodiment 3, be benchmark with the gross weight of slag supplying agent, the content of CaO is 48 weight %, said SiO
2Content be 4 weight %, said Al
2O
3Content be 36 weight %, the content of said MgO is 3.5 weight %, Al content 8.5 weight %.
Said covering slag contains CaO, SiO
2, Al
2O
3, Na
2O, CaF
2And C, be benchmark with the gross weight of covering slag, the content of said CaO is 36 weight %, said SiO
2Content be 40 weight %, said Al
2O
3Content be 4 weight %, said Na
2The content of O is 8 weight %, said CaF
2Content be 8 weight %, the content of said C is 4 weight %.
Embodiment 1
Present embodiment is used to explain the preparation of ultra low-carbon steel provided by the invention and ultra low-carbon steel sheet material.
This embodiment adopts method of the present invention to control IF3 trade mark ultra-deep punching cold-rolling steel sheet streak shape defective, and IF3 trade mark extra-deep drawing steel chemical composition is seen table 1 (unit: weight %).
The IF3 steel converter adds basicity (CaO/SiO after smelting in the tapping process
2Weight ratio) be that 84 refining slag and molten steel mix and dash; Add-on is 5.0 kg/ton molten steel, and (Mn content is 80 weight %, and Fe content is 18.5 weight % to add mid-carbon fe-mn at the bag end simultaneously; C content is 1.4 weight %; S content is 0.01 weight %) 2.3 kg/ton molten steel carry out preliminary dexidation, and making the gross weight with molten steel is benchmark, makes that the activity oxygen level is that 0.045 weight %, S content are 0.010 weight % in the molten steel; After tapping finished, adding metal A l content at the ladle slag top of the slag was the reductibility slag supplying agent of 10 weight %, and add-on is 4.5 kg/ton molten steel, reduces the ladle slag oxidisability; After (temperature is about 1630 ℃) handled in temperature adjustment through the LF stove, after RH vacuum unit (molten steel weight is 120 tons) carries out decarburization and alloy fine setting, the molten steel vacuum cycle time was controlled at 7 minutes; Pressure 100 handkerchiefs, the flow of argon gas is 1250 liters/minute, obtaining C content is 0.0045 weight %; Si content is 0.01 weight %, and Mn content is 0.15 weight %, and P content is 0.01 weight %; S content is 0.01 weight %; Ti content is 0.065 weight %, and Als is the molten steel of 0.04 weight %, and surplus is an iron; Open at continuous casting working procedure and wide cooling water inflow of mold to be set at 2932 liters/minute square metres before watering, the leptoprosopy water yield is set at 2111 liters/minute square metres, opens in mold, to push basicity (CaO/SiO rapidly after watering
2) be 0.90, fusing point is 1080 ℃ crystallizer protecting residue; This covering slag is 0.28Pas 1300 ℃ viscosity; And the casting machine pulling rate improved and stable (cooling range is 6.9 ℃ to 1.2 meters/minute; When stable pulling rate was 1.2 meters/minute, wide, leptoprosopy mean heat flux were respectively 1405 kilowatts/square metre and 1166 kilowatts/square metre, and the hot-fluid ratio is 0.83); After using above measure, the molten steel sulphur content is reduced to 0.010 weight % after refining finishes by the 0.018 weight % in when tapping, and the desulfurization in refining process rate reaches 44.45%; Based on the gross weight of ladle slag, (FeO+MnO) content is reduced to 18.5 weight % after refining finishes by 40.25 weight % after tapping in the ladle slag; After the RH refining in the steel T [O] content reduce to 0.0025 weight % by 0.005 weight %; The consumption of covering slag is determined as 0.5 kg/ton molten steel, level fluctuation scope 0-3 millimeter in the casting process mold.After casting finishes; With the thickness of producing is that 200 millimeters strands are randomly drawed 10; Hand inspection cc billet surface quality situation, dig 3 millimeters simultaneously along the sample of long 500 millimeters of strand length direction intercepting, and with its surface after the subcutaneous quality of inspection; The result shows that casting billet surface does not have longitudinal crack, transverse crack, transverse corner crack line, subcutaneous no map cracking.
The strand of producing is become zinc-plated lath finished product through hot rolling with cold rolling, the strip defective is not seen in the check of finished product, product qualified rate is 100%.
Table 1
| C | Si | Mn | P | S | Als | Ti |
| ?≤0.005 | ≤0.03 | 0.10-0.25 | ?≤0.015 | ?≤0.015 | 0.02-0.07 | 0.050-0.085 |
Embodiment 2
Present embodiment is used to explain the preparation of ultra low-carbon steel provided by the invention and ultra low-carbon steel sheet material.
This embodiment controls IF4 trade mark ultra-deep punching cold-rolling steel sheet streak shape defective for adopting method of the present invention, and IF4 trade mark extra-deep drawing steel chemical composition is seen table 2 (unit: weight %).
The IF4 steel converter adds basicity (CaO/SiO after smelting in the tapping process
2) 95 high basicity refining slag and molten steel mix and dash; Add-on is 6.0 kg/ton molten steel, and (Mn content is 80 weight %, and Fe content is 18.5 weight % to add mid-carbon fe-mn at the bag end simultaneously; C content is 1.4 weight %; S content is 0.01 weight %) 2.2 kg/ton molten steel carry out preliminary dexidation, and making the gross weight with molten steel is benchmark, makes that oxygen activity is that 0.038 weight %, S content are 0.008 weight % in the molten steel; After tapping finished, adding metal A l content at the ladle slag top of the slag was the reductibility slag supplying agent of 11.5 weight %, and add-on is 6 kg/ton molten steel; After (temperature is about 1620 ℃) handled in temperature adjustment through the LF stove, after the RH vacuum unit carries out decarburization and alloy fine setting, be controlled at 6 minutes pressure 50 handkerchiefs the molten steel vacuum cycle time; The flow of argon gas is 1250 liters/minute, and obtaining C content is 0.004 weight %, and Si content is 0.005 weight %; Mn content is 0.2 weight %, and P content is 0.014 weight %, and S content is 0.008 weight %; Ti content is 0.055 weight %, and Als is the molten steel of 0.06 weight %, and surplus is an iron; Open at continuous casting working procedure and wide cooling water inflow of mold to be set at 2934 liters/minute square metres before watering, the leptoprosopy water yield is set at 2122 liters/minute square metres, opens in mold, to push basicity (CaO/SiO rapidly after watering
2) be 0.95, fusing point is 1100 ℃ crystallizer protecting residue; This covering slag is 0.22Pas 1300 ℃ viscosity; And within a short period of time with the casting machine pulling rate improve, it is stable that (cooling range is 6.75 ℃ to 1.1 meters/minute; When stable pulling rate was 1.1 meters/minute, wide, leptoprosopy mean heat flux were respectively 1382 kilowatts/square metre and 1145 kilowatts/square metre, and the hot-fluid ratio is 0.83); After using above measure, the molten steel sulphur content by when tapping 0.022 weight % reduce to refining and finish back 0.009 weight %, the desulfurization in refining process rate reaches 59.09%; Based on the gross weight of ladle slag, (FeO+MnO) content is reduced to 15 weight % by 38.5 weight % after tapping in the ladle slag; After the RH refining in the steel T [O] content reduce to 0.002 weight % after refining finishes by 0.0048 weight %; The consumption of covering slag is determined as 0.55 kg/ton molten steel, level fluctuation scope 0-2 millimeter in the casting process mold.After casting finishes; The strand of producing (thickness is 200 millimeters) is randomly drawed 10; Hand inspection cc billet surface quality situation, dig 3 millimeters simultaneously along the sample of long 500 millimeters of strand length direction intercepting, and with its surface after the subcutaneous quality of inspection; The result shows that casting billet surface does not have longitudinal crack, transverse crack, transverse corner crack line, subcutaneous no map cracking.
The strand of producing is become zinc-plated lath finished product through hot rolling with cold rolling, the strip defective is not seen in the check of finished product, product qualified rate is 100%.
Table 2
| C | Si | Mn | P | S | Als | Ti |
| ?≤0.004 | ≤0.03 | 0.10-0.25 | ?≤0.015 | ?≤0.015 | 0.02-0.06 | 0.050-0.085 |
Embodiment 3
Present embodiment is used to explain the preparation of ultra low-carbon steel provided by the invention and ultra low-carbon steel sheet material.
This embodiment controls IF4 trade mark ultra-deep punching cold-rolling steel sheet streak shape defective for adopting control method of the present invention.
The IF4 steel converter adds basicity (CaO/SiO after smelting in the tapping process
2) 90 high basicity refining slag and molten steel mix and dash; Add-on is 5 kg/ton molten steel, and (Mn content is 80 weight %, and Fe content is 18.5 weight % to add mid-carbon fe-mn at the bag end simultaneously; C content is 1.4 weight %; S content is 0.01 weight %) 2.3 kg/ton molten steel carry out preliminary dexidation, and making the gross weight with molten steel is benchmark, makes that oxygen activity is that 0.040 weight %, S content are 0.008 weight % in the molten steel; After tapping finished, adding metal A l content at the ladle slag top of the slag was the reductibility slag supplying agent of 8.5 weight %, and add-on is 4.5 kg/ton molten steel; After (temperature is about 1630 ℃) handled in temperature adjustment through the LF stove, after the RH vacuum unit carries out decarburization and alloy fine setting, the molten steel vacuum cycle time was controlled at 5 minutes; Pressure 80 handkerchiefs, the flow of argon gas is 1250 liters/minute, obtaining C content is 0.004 weight %; Si content is 0.015 weight %, and Mn content is 0.20 weight %, and P content is 0.008 weight %; S content is 0.012 weight %, and Ti content is 0.075 weight %, and Als is the molten steel of 0.03 weight %; Open at continuous casting working procedure and wide cooling water inflow of mold to be set at 2934 liters/minute square metres before watering, the leptoprosopy water yield is set at 2122 liters/minute square metres, opens in mold, to push basicity (CaO/SiO rapidly after watering
2) be 1.10, fusing point is 1080 ℃ crystallizer protecting residue; This covering slag is 0.2Pas 1300 ℃ viscosity; And within a short period of time with the casting machine pulling rate improve, it is stable that (cooling range is 6.6 ℃ to 0.9 meter/minute; When stable pulling rate was 0.9 meter/minute, wide, leptoprosopy mean heat flux were respectively 1352 kilowatts/square metre and 1134 kilowatts/square metre, and the hot-fluid ratio is 0.84); After using above measure, the molten steel sulphur content by when tapping 0.016 weight % reduce to refining and finish back 0.008 weight %, the desulfurization in refining process rate reaches 50%; (FeO+MnO) content is reduced to 18 weight % after refining finishes by 42.75 weight % after tapping in the ladle slag; After the RH refining in the steel T [O] content reduce to 0.0026 weight % by 0.0042 weight %; The consumption of covering slag is determined as 0.6 kg/ton molten steel, level fluctuation scope 0-2 millimeter in the casting process mold.After casting finishes; The strand of producing (thickness is 200 millimeters) is randomly drawed 10; Hand inspection cc billet surface quality situation, dig 3 millimeters simultaneously along the sample of long 500 millimeters of strand length direction intercepting, and with its surface after the subcutaneous quality of inspection; The result shows that casting billet surface does not have longitudinal crack, transverse crack, transverse corner crack line, subcutaneous no map cracking.
The strand of producing is become zinc-plated lath finished product through hot rolling with cold rolling, the strip defective is not seen in the check of finished product, product qualified rate is 100%.
Comparative Examples 1
This Comparative Examples is used to explain the preparation of the ultra low-carbon steel and the ultra low-carbon steel sheet material of prior art.
This Comparative Examples adopts existing method to prepare IF3 trade mark ultra low-carbon steel cold-rolled steel sheet.
After the IF4 steel converter is smelted; In the tapping process, (Mn content is 80 weight %, and Fe content is 18.5 weight % to add mid-carbon fe-mn at the bag end; C content is 1.4 weight %; S content is 0.01 weight %) 2.3 kg/ton molten steel carry out preliminary dexidation, and making the gross weight with molten steel is benchmark, makes that the activity oxygen level is that 0.065 weight %, S content are 0.015 weight % in the molten steel; After tapping finishes, after (temperature is about 1630 ℃) handled in temperature adjustment through the LF stove, after the RH vacuum unit carries out decarburization and alloy fine setting; Obtaining C content is 0.0050 weight %, and Si content is 0.020 weight %, and Mn content is 0.25 weight %; P content is 0.014 weight %, and S content is 0.015 weight %, and Ti content is 0.075 weight %; Als is the molten steel of 0.02 weight %, and surplus is an iron, opens at continuous casting working procedure and wide cooling water inflow of mold is set at 3765 liters/minute square metres before watering; The leptoprosopy water yield is set at 2744 liters/minute square metres, opens in mold, to push basicity (CaO/SiO rapidly after watering
2) be 1.05, fusing point is 960 ℃ crystallizer protecting residue; This covering slag is 0.08Pas 1300 ℃ viscosity; And within a short period of time the casting machine pulling rate is improved and stable to 1.6 meters/minute (when stablizing pulling rate and being 1.6 meters/minute; Cooling range is 5.9 ℃, and wide, leptoprosopy mean heat flux are respectively 1556 kilowatts/square metre and 1447 kilowatts/square metre, and the hot-fluid ratio is 0.93).After using above measure, the molten steel sulphur content by when tapping 0.016 weight % reduce to refining and finish back 0.008 weight %, refining process is failed desulfurization; (FeO+MnO) content reaches 40 weight % in the ladle slag; After the RH refining in the steel T [O] content be 0.004 weight %; The consumption of covering slag is determined as 0.9 kg/ton molten steel, level fluctuation scope 2-9 millimeter in the casting process mold.After casting finishes; The strand of producing (thickness is 200 millimeters) is randomly drawed 10; Hand inspection cc billet surface quality situation; The subcutaneous quality of inspection after digging 3 millimeters simultaneously along the sample of long 500 millimeters of strand length direction intercepting, and with its surface, it is darker that the result shows that transverse crack, transverse corner crack line and subcutaneous map cracking have appearred in casting billet surface.
The strand of producing is become zinc-plated lath finished product through hot rolling with cold rolling, a large amount of strip defectives are found in the check of finished product, product qualified rate is 40%.
Can find out that from the result of above embodiment 1-3 and Comparative Examples 1 continuously cast bloom surface and the subcutaneous quality of using method production provided by the invention to obtain are good, the ultra low-carbon steel galvanized sheet that makes does not have the strip defective, and qualification rate is 100%.
Claims (9)
1. the preparation method of a ultra low-carbon steel, this method comprises:
(1) molten steel that smelting is obtained carries out external refining, and the method for said external refining comprises carries out preliminary dexidation alloying and desulfurization with molten steel, and making molten steel activity oxygen level is that 0.04-0.06 weight %, S content are 0.008-0.015 weight %; And molten steel carried out temperature adjustment processing and decarburization and alloy fine setting, and making the gross weight with molten steel is benchmark, to be respectively C content be 0.003-0.005 weight % to each substances content in the molten steel; Si content is 0.002-0.03 weight %, and Mn content is 0.1-0.25 weight %, and P content is 0.006-0.015 weight %; S content is 0.006-0.015 weight %; Ti content is 0.050-0.085 weight %, and Als is 0.02-0.08 weight %, and surplus is an iron;
(2) molten steel after the external refining is carried out continuous casting, the method for said continuous casting comprises the molten steel after the external refining is injected in the mold continuously, and in mold, adds covering slag; Through mold cooling, make the molten steel surface duricrust that congeals into, the outlet of this molten steel with duricrust from mold pulled straight, make it cool off and all solidify with the straightening district at secondary cooling zone, the outlet in the straightening district obtains continuously cast bloom;
It is characterized in that; In step (1), molten steel is carried out after preliminary dexidation alloying and the desulfurization, before temperature adjustment handles, adds the slag supplying agent that Al content accounts for slag supplying agent gross weight 8-12% at the ladle slag top of the slag; Make in the ladle slag based on the gross weight of ladle slag, (FeO+MnO) content is≤20 weight %; And after decarburization and alloy fine setting, molten steel is circulated under vacuum condition, the feasible gross weight with steel of the condition of vacuum cycle is a benchmark, T in the steel [O] content is 0.0025-0.004 weight %;
In step (2), the viscosity of said covering slag in the time of 1300 ℃ is 0.2-0.3PaS, and basicity is 0.8-1.1, and fusing point is 1040-1130 ℃; It is 1350-1416 kilowatt/square metre that cooling crystallizer makes the heat flow density of wide of mold, and the heat flow density of leptoprosopy is 1122-1174 kilowatt/square metre, and mold leptoprosopy and wide heat flow density are than being 0.8-0.85; The pulling rate that the said molten steel that will have a duricrust pulls straight from the outlet of mold be 0.8-1.3 rice/minute.
2. method according to claim 1, wherein, said slag supplying agent contains CaO, SiO
2, Al
2O
3, MgO and Al, be benchmark with the gross weight of this slag supplying agent, the content of said CaO is 40-50 weight %, said SiO
2Content be 4-6 weight %, said Al
2O
3Content be 35-45 weight %, the content of said MgO is 2-4 weight %, the content of said Al is 8-12 weight %; The consumption of said slag supplying agent is a 4-6 kg/ton molten steel.
3. method according to claim 1 wherein, is carried out molten steel circulating in the RH vacuum unit under vacuum condition, and the pressure in the said RH vacuum unit is the 50-100 handkerchief; Argon gas be blown into intensity be molten steel 8-12 liter per ton/minute, the vacuum cycle time is 5-7 minute.
4. method according to claim 1, wherein, said covering slag contains CaO, SiO
2, Al
2O
3, Na
2O, CaF
2And C, be benchmark with the gross weight of this covering slag, the content of said CaO is 25-40 weight %, said SiO
2Content be 28-40 weight %, said Al
2O
3Content be 2-6 weight %, said Na
2The content of O is 6-10 weight %, said CaF
2Content be 3-10 weight %, the content of said C is 2-10 weight %.
5. method according to claim 1; Wherein, The method of cooling crystallizer comprises the water quench mold with 20-40 ℃; On the unit surface, wide cooling water inflow of mold be the 1540-4115 liter/minute square metre, the leptoprosopy cooling water inflow of mold be the 1385-3889 liter/minute square metre.
6. according to claim 1 or 5 described methods, wherein, on the unit surface, wide cooling water inflow of mold be the 2920-2942 liter/minute square metre, the leptoprosopy cooling water inflow of mold be the 2050-2170 liter/minute square metre.
7. method according to claim 1, wherein, it is that the refining slag of 80-100 mixes with molten steel that the method for said preparatory desulfurization comprises basicity, the consumption of said refining slag is a 4-6 kg/ton steel.
8. method according to claim 7, wherein, said refining slag contains fluorite and quickened lime, is benchmark with the total amount of refining slag, and the content of said quickened lime is 70-85 weight %, and the content of said fluorite is 15-30 weight %.
9. the preparation method of a ultra low-carbon steel sheet material, this method comprises rolling ultra low-carbon steel strand, it is characterized in that, said ultra low-carbon steel strand is for to be made by any described method among the claim 1-8.
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