CN1270862A - Protective scoria for continuous casting of ultralow carbon steel - Google Patents
Protective scoria for continuous casting of ultralow carbon steel Download PDFInfo
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- CN1270862A CN1270862A CN 00107260 CN00107260A CN1270862A CN 1270862 A CN1270862 A CN 1270862A CN 00107260 CN00107260 CN 00107260 CN 00107260 A CN00107260 A CN 00107260A CN 1270862 A CN1270862 A CN 1270862A
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Abstract
The present invention relates to the treatment of molten ferroalloy and continuous casting of metal. The protective scoria for continuous casting has the chemical components in mass percengate of: Na2O 6-10, F- 7-10, Al2O3 2-8, MgO 2-5, one or two of FeO, Fe3O4 and Fe2O3 3.1-15, C 1.0-1.5, and the rest being CaO and SiO2 in the CaO/SiO2 ratio of 0.70-0.89. It is hollow grains in size of 0.7-1.08 mm. When it is used in continuous casting of ultralow carbon steel, it results in very low carbon increment.
Description
The present invention relates to the field of treatment of molten iron alloy and continuous casting of metal, and is especially suitable for continuous casting crystallizer and casting of carbon content [% (m/m)]At 5X 10-3The following ultra-low carbon steel.
The carbon material is usually matched in the covering slag for continuous casting, and the proper carbon material can control the melting speed of the slag, so that the reasonable thicknesses of a powder slag layer, a semi-molten layer and a molten slaglayer are kept above a crystallizer, the spreading performance of the covering slag is improved, the covering slag is not hardened, and the like, thereby obtaining a good casting blank surface. It can be said that carbon plays an extremely important and difficult-to-replace role in the use of mold flux. However, the carbon content of the mold flux often causes the recarburization of molten steel, and the recarburization amount has little influence on the casting of general carbon steel, but the carbon content is 5 x 10 for the casting-3% or less of ultra-low carbon steel often causes molten steel of 1.5 to 3X 10-3% of recarburization can not meet the performance requirement of the ultra-low carbon steel continuous casting billet.
In the prior art, the recarburization problem of the mold flux is generally solved by adopting the following methods:
(1) the content of free carbon in the mold flux is reduced. The original carbon content of the covering slag for the continuous casting of the ultra-low carbon steel is controlled to be below 2 percent mostly. However, since the content of carbon is reduced, the separation effect of carbon on the base material is weakened, the melting speed of the mold flux is increased, the slag layer is too thick, and the defects of slag inclusion and longitudinal cracking on the surface of a casting blank are easily caused.
(2) A method of changing the carbonaceous material is adopted, for example, a carbon black type carbonaceous material or activated carbon having a low combustion temperature and a high combustion speed is used. However, the carbon black cannot avoid the formation of a carbon-rich layer, and the combustion speed of the activated carbon is too high, so that a semi-molten layer and a slag layer are hardly formed, and the carbon black cannot play a role of the mold flux.
(3) The original carbon content is 1%, and strong reducing substances such as Ca-Si, Fe-Mn, Al, etc. (Japanese patent laid-open Nos. 52-57028 and 55-128526) are added. Because the strong reducing substance preferentially reacts with oxygen in the melting process, the carbon in the casting powder is protected, the defects of casting blanks caused by low carbon content in the powder and the too fast melting of the casting powder are avoided, and the recarburization is not caused. However, if these strongly reducing substances are not completely oxidized, impurities of steel are easily generated.
(4) Using nitrides having a crystal structure similar to that of graphite, e.g. BN, SiN3、Cr3And replacing the carbonaceous materials (Japanese patent laid-open Nos. 51-147432 and 52-57030) with N to prepare the carbon-free mold flux. Usually makeBN, however, is relatively costly due to the formation of B2O3To release N2The slag surface is often subjected to bubbling and expansion, and the casting powder is easy to harden due to no carbon, so that the process is difficult to popularize up to now.
(5) By adding oxidizing agents, e.g. MnO, to the casting powder2(JP-A6-198403) or rolled iron sheet powder (ZL 97121944.3). But MnO of2Easily extends into the long nozzle together with the fused quartz to generate MnSiO with low melting point3(multiflora rose pyroxene) or Mn2SiO4(fayalite) to affect the growth of waterThe service life of the port. In addition, the addition amount of the rolled steel skin powder is only controlled to be 1-3%, which is not enough to fully oxidize the carbon of the enriched carbon layer, and the carburization amount [% (m/m) of the casting blank]Is still 6X 10-4。
The invention aims to provide a casting powder for continuous casting of ultra-low carbon steel, which is not only provided with indispensable carbon, but also does not cause recarburization of molten steel, and has simple manufacturing process.
First, there are two main reasons for analyzing the recarburization of molten steel caused by mold flux used in a mold. One is to join in the covering slag, wrap up by the liquid bead in the slagging process, carbon that is not completely burnt because of the oxygen deficiency, along with the increase and the polymerization of liquid slag, because its proportion is less than the liquid slag and constantly floats, gather in the interface top of slag layer and semi-molten layer to form 0.3 ~ 0.5mm thick, the carbon content is higher than original carbon content 1.5 ~ 10 times, the enrichment carbon bed that is higher even. If the thickness of the slag layer is insufficient, the molten steel is very easy to contact with the enriched carbon layer as long as the liquid level of the continuous casting crystallizer fluctuates slightly, and carbon is an element which is very soluble in the molten steel at high temperature, so that the recarburization of a casting blank is inevitably caused. Secondly, carbon has certain solubility in a slag layer, and in the process of melting the casting powder, along with the occurrence and continuous increase of liquid slag, a small part of carbon in the slag is absorbed by the molten slag, usually the carbon content of the molten slag reaches 0.06-0.13 percent or even higher, the carbon in the slag layer diffuses into the molten steel through the interface of the slag layer and the molten slag steel, the diffusion coefficient of the carbon is related to the performance of the molten slag, particularly the viscosity of the molten slag, if the viscosity of the molten slag is lower, the carbon directly contacts with the molten steel at about 1500 ℃, the carbon content of the slag layer is higher by one order of magnitude than that of the molten steel with ultralow carbon, and the carbon contentof the slag layer is undoubtedly one of the other main reasons for causing the carburization of casting blanks.
Aiming at the reason that the casting blank is carburized due to the covering slag, the covering slag is prepared from CaO and SiO2As base material, with Na2O、F-、Al2O3MgO is fluxing agent, ferric oxide is oxygen supply agent, and C is melting speed regulator. The specific chemical composition is [% (m/m)]：Na2O is 6 to 10, F-7 to 10, Al2O32 to 8, MgO 2 to 5, FeO, Fe3O4、Fe2O3Any one or the sum of any two of the above is 3.1-15, C is 1.0-1.5, and the rest is CaO and SiO2，CaO/SiO20.70 to 0.89.
The covering slag of the invention is made of CaO and SiO2CaO/SiO as base material for controlling basicity of protecting slag20.70 to 0.89, so that the viscosity of the mold flux at 1300 ℃ is 0.2 to 0.5 Pa.S. The main purpose of the utility model is that,the ultra-low carbon steel has poor heat-conducting property, the general blank drawing speed is slow, the thickness of a slag layer is easy to reduce, and once the operation is unstable, molten steel is easy to contact with a carbon-enriched layer to increase carbon. The viscosity of the casting powder is properly improved, the slag consumption is reduced, and the liquid slag layer is thickened. Meanwhile, the diffusion speed of carbon in the slag layer to molten steel is greatly reduced due to the increase of the viscosity of the slag layer. If CaO/SiO2If the viscosity of the casting powder is less than 0.70, the viscosity of the casting powder at 1300 ℃ is more than 0.5Pa.S, and the slag layer is excessively viscous, so that the lubrication and filling properties of the casting powder are influenced, and the surface longitudinal crack defect of the casting blank is caused. If CaO/SiO2If the temperature is higher than 0.89 ℃, the viscosity of the protective slag at 1300 ℃ is less than 0.2Pa.S, the molten slag is too dilute, and the diffusion coefficient of carbon in a molten slag layer to molten steel is increased.
In the mold flux of the invention, Na2O and F-mainly play a role in lowering the melting temperature, and too high or too low not only plays a role in regulating the melting temperature but also causes surface defects of the casting blank. Thus, Na2O should be controlled to 6-10%, F-Should be controlled to be 7-10%. In the mold flux of the invention, Al2O3Can also adjust the melting temperature of the casting powder, but improves Al2O3In an amount that increases the slag viscosity, and Al2O3The content is too high, and the covering slag absorbs Al in the molten steel2O3The inclusion capacity is unfavorable, so the content should be controlled to be 2-8%. In the casting powder, MgO can play a role in reducing the melting temperature of the casting powder and enabling the casting powder to be melted uniformly, but the content of MgO cannot be too high, otherwise, insoluble periclase and the like are easily generated, and therefore, the content is controlled to be 2-5%. The comprehensive effect of meeting and adjusting the content conditions of the fluxing agents is to ensure that the melting temperature of the casting powder is higherAt 1080. + -. 15 ℃.
In the mold flux of the present invention, an oxidizing agent such as FeO, Fe is added in a certain amount separately3O4、Fe2O3The main purpose of the oxidizing agent is that the oxidizing agent can play a role in promoting the oxidation of unburned carbon in the casting powder and reducing the carbon content of the enriched carbon layer. With Fe2O3For example, the following reaction:
FeO、Fe3O4、Fe2O3The content of any one or the sum of the two should be controlled to be 3.1-15%, the content of carbon in the enriched carbon layer is not obviously reduced and is higher than 15%, and the melting temperature of the protective slag is excessively reduced and exceeds the range of 1080 +/-15 ℃.
Although the iron oxide content in the mold flux exceeds 3%, there is no fear that the iron oxide will transfer oxygen into the steel. Because only Fe in the slag is present2O3Combined with CaO to CaO&Fe2O3(calcium ferrite) in the slagOxygen transfer occurs only at the interface with the molten steel:
Under the condition of meeting the conditions, the casting powder disclosed by the invention selects the carbon black as a melting speed regulator, because the carbon black type carbon material has small particle size, the separation capability on a base material and the retardation effect on the flowing and gathering of a melt are strong, and when the original carbon content is low, the melting speed of the casting powder is favorably delayed, and the over-thickness of a slag layer is avoided. In addition, when the carbon black type carbonaceous material is used, the carbon content of the slag layer and the carbon-rich layer is reduced. The original carbon content is controlled to be 1.0-1.5%, and the problems are not caused although the carbon content is low.
The covering slag is hollow granular slag, raw materials are stirred in a vortex stirring device, atomized and formed in a spray drying washing tower and dried to prepare the hollow granular slag with the granularity of 0.7-1.08 mm.
Compared with the prior art, the invention has the following advantages:
(1) the slag has lower melting temperature and higher viscosity, and can form proper thickness of a slag layer and reduce the thickness of the slag layer
The coefficient of diffusion of carbon in the slag layer to the molten steel is reduced, and the molten steel is slightly carburized.
(2) The slag contains a certain amount of oxidant to fully oxidize the carbon in the enriched carbon layer, thereby reducing the content of carbon in the enriched carbon layer
The enriched carbon layer increases the carbon possibility to the molten steel, and does not cause the oxygenation of the molten steel, so as to increase the carbon of the molten steel
And very little.
(3) Although the carbon content in the slag is low, the problems of over-thick slag layer, slag hardening and the like do not occur, and thecasting powder
Good spreadability in the crystallizer and active slag surface.
(4) The mold flux does not corrode a fused silica nozzle during casting.
Drawings
FIG. 1 shows Fe in the mold flux2O3Influence of the content on the carbon content of the carbon-enriched layer
FIG. 2 shows the measurement of Fe in the mold flux for obtaining a melting model2O3The effect of the content on the carbon content of the enriched carbon layer
The structure of the one-way heating furnace is schematically shown.
In FIG. 1, the ordinate represents Fe in slag2O3Content [% (m/m)]The abscissa is the value of the melting point
The carbon content [% (m/m)]of the carbon-collecting layer.
In fig. 2, 1 is a slag layer, 2 is a semi-molten layer, 3 is an enriched carbon layer, 4 is a slag layer, 5 is a refractory material, 6 is a heating body, 7 is a crucible, and 8 is a thermocouple. The crucible 7 is arranged above the heating body 6 of the heating furnace, and the thermocouple 8 is arranged at the bottom of the crucible 7.
Examples
Example 1
In the one-way heating furnace shown in FIG. 2, a melting model experiment was performed to measure Fe2O3The effect of the content on the carbon content in the carbon rich layer. Firstly, preparing experimental base slag, wherein the components of the experimental base slag are [% (m/m)]Comprises the following steps: na (Na)2O is 9, F-Is 8.5, Al2O34.5, 3.5 for MgO, 34.17 for CaO, SiO238.83 percent and 1.5 percent of C, and then adding Fe with different contents of 3 percent, 5 percent, 8 percent, 10 percent and 15 percent into the base slag respectively2O3And mixing with the basic slag to prepare five experimental slags. Putting the corundum crucible into a one-way heating furnace, heating along with the furnace, keeping the temperature constant when the temperature of the bottom of the crucible reaches 1450 ℃, and then adding 3% of Fe2O3The experimental slag is poured into a crucible, the crucible is taken out after 10 minutes to obtain a melting model, an enriched carbon layer is separated, and the carbon content of the enriched carbon layer is analyzed. The other four experimental slags are determined by the same method, and Fe is drawn2O3The results are shown in figure 1, which is a plot of content versus carbon content of the enriched carbon layer. As can be seen from FIG. 1, Fe is added to the slag2O3The content of carbon in the enriched carbon layer is obviously reduced due to the increase of the amount, and Fe is added into the slag2O3Less than 3%, the carbon content of the enriched carbon layer is not obviously reduced, and when Fe is contained in the slag2O3At 15% addition, the carbon rich layer disappeared. Therefore, the casting powder can control the recarburization of the ultra-low carbon steel in continuous casting.
Example 2
The contact experiment of the ultra-low carbon steel covering slag and steel slag is carried out in a conventional carbon tube furnace. 500g of industrial pure iron (with a carbon content of 0.005%) was placed in a corundum crucible and then in a carbon tube furnace, the temperature was raised to 1550 ℃ (argon gas was passed through), after the steel wasmelted, 50g of the slag of example 2 (see table 1 for the components) was added, and after 3 minutes the crucible was removed from the furnace and cooled, and the carbon content in the upper, middle and lower portions of the steel sample was analyzed. Comparative example 1 the slag (composition shown in table 1) was measured by the same method. The main properties of slag and the carburization results in contact with molten steel are shown in Table 2. As can be seen from Table 2, it contains 3% Fe2O3And 1.2 percent FeO, the slag of the example 2 with larger viscosity and high carbon content has one order of magnitude lower carbon content than the slag of the comparative example 1 which does not contain ferric oxide, has smaller viscosity and low carbon content.
Example 3
Casting experiments of mold fluxes of example 3, comparative example 2, and comparative example 3 were performed in the mold of the slab caster. The compositions of the mold fluxes of example 3, comparative example 2 and comparative example 3 are shown in Table 1, and the cast steel type has a carbon content of less than 5X 10-3% of ultra-low carbon steel, taking a tundish steel sample during casting, taking a casting blank sample at a casting blank position corresponding to the time when the tundish steel sample is taken after the casting is finished, respectively analyzing the carbon content of the casting blank sample, and taking the difference between the carbon content and the carbon content as the carbon increment of the casting blank caused by the casting powder in the casting process. Table 3 shows the main properties of the mold flux of example 3, comparative example 2 and comparative example 3 and the results of the mold flux causing the carburization of the cast slab in the casting test. As can be seen from the results, the amount of carburization of molten steel was not more than 3X 10 using the mold flux of the present invention-4Percent can meet the quality requirement of continuous casting billets, and the carbon increment of the casting billets in the comparative example is (6-10) multiplied by 10-4% of the total weight of the composition. In addition, the casting powder in the example 3 has good spreadability in the crystallizer, active slag surface, no hardening, no slag strip or slag block formation, no erosion of a water gap, smooth casting blank surface, no crack, no slag inclusion and other defects.
TABLE 1 chemical composition [% (m/m) of mold flux of examples and comparative examples]
TABLE 2 main properties of the slags of example 2 and comparative example 1 and the results of the carburization in the steel slag contact test
TABLE 3 main properties of slag of example 3 and comparative examples 2 and 3 and the results of recarburization of casting slab by mold flux
| Item | Chemical composition [% 1m/m)] | |||||||||||
| CaO | SiO2 | Na2O | F- | Al2O3 | MgO | C | Fe3O4 | Fe2O3 | FeO | Ca-Si | Li2O | |
| Practice of Example (b) | 32.3 | 38.0 | 8.5 | 8.0 | 4.0 | 3.5 | 1.5 | 3.5 | 0.7 | |||
| Practice of Example (b) | 31.34 | 39.18 | 9.45 | 7.97 | 4.12 | 3.01 | 1.49 | 1.0 | 2.44 | |||
| Comparison Example (b) 1 | 39.43 | 42.45 | 9.04 | 4.26 | 3.13 | 1.22 | 1.0 | 3.5 (additionally) | ||||
| Comparison Example (b) 2 | 28.98 | 35.24 | 10.54 | 8.84 | 3.12 | 1.36 | 1.42 | The balance of carbonic acid Root and impurities | ||||
| Comparison Example (b) 3 | 33.71 | 34.17 | 11.98 | 6.80 | 4.93 | 2.52 | 2.5 | 2.87 | 0.52 | |||
Claims (2)
1. The covering slag for continuous casting of ultra-low carbon steel is characterized by comprising the following chemical components in percentage (m/m)]Comprises the following steps: na (Na)2O is 6 to 10, F-7 to 10, Al2O32 to 8, MgO 2 to 5, FeO, Fe3O4、Fe2O3Any one or the sum of any two of the above is 3.1-15, C is 1.0-1.5, andthe rest is CaO and SiO2，CaO/SiO20.70 to 0.89.
2. The mold flux according to claim 1, characterized in that the mold flux is a hollow granular flux having a particle size of 0.7 to 1.08 mm.
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| CN 00107260 CN1131118C (en) | 2000-04-30 | 2000-04-30 | Protective scoria for continuous casting of ultralow carbon steel |
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| CN 00107260 CN1131118C (en) | 2000-04-30 | 2000-04-30 | Protective scoria for continuous casting of ultralow carbon steel |
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| CN1270862A true CN1270862A (en) | 2000-10-25 |
| CN1131118C CN1131118C (en) | 2003-12-17 |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318165C (en) * | 2004-02-27 | 2007-05-30 | 宝山钢铁股份有限公司 | Coverage dregs for ladle |
| CN1321764C (en) * | 2004-06-23 | 2007-06-20 | 青岛斯多伯格三一冶金材料有限公司 | Fluorine free protecting slag for steelmaking and continuous casting and method for manufacturing same |
| CN100443215C (en) * | 2006-08-25 | 2008-12-17 | 重庆大学 | Protective slag for ultralow carbon steel continuous casting |
| CN1788880B (en) * | 2004-12-14 | 2010-08-11 | 上海盘龙实业有限公司 | Dual-functional composite solid protective slag for stainless steel die casting |
| CN101612653B (en) * | 2008-06-23 | 2011-04-13 | 宝山钢铁股份有限公司 | Mold powder for continuous casting of high aluminium-titanium-rare earth steel |
| CN101612652B (en) * | 2008-06-23 | 2011-06-15 | 宝山钢铁股份有限公司 | Mold powder for continuous casting of low nickel and high manganese stainless steel and preparation method thereof |
| CN101773996B (en) * | 2010-01-21 | 2012-05-30 | 山西太钢不锈钢股份有限公司 | Continuous casting crystallizer covering slag for non-interstitial atom steel |
| CN101637811B (en) * | 2009-08-11 | 2012-06-06 | 河南省西保冶材集团有限公司 | Continuous casting functional protective material specially used for high pressure oil well pipe |
| CN103121089A (en) * | 2013-03-12 | 2013-05-29 | 西峡龙成冶金材料有限公司 | Colorful continuous casting crystallizer covering slag for ultra-low carbon steel |
| CN104399921A (en) * | 2014-11-13 | 2015-03-11 | 北京首钢股份有限公司 | Casting powder |
| CN104511580A (en) * | 2013-09-30 | 2015-04-15 | 上海梅山钢铁股份有限公司 | Molten steel solvent for low-carbon steel |
| CN106513606A (en) * | 2016-12-30 | 2017-03-22 | 西峡龙成冶金材料有限公司 | Continuous casting crystallizer covering slag special for IF steel |
| CN106694833A (en) * | 2016-12-28 | 2017-05-24 | 西峡龙成冶金材料有限公司 | Crystallizer covering slag special for CSP thin slab continuous casting medium carbon steel |
| CN107282903A (en) * | 2016-12-30 | 2017-10-24 | 西峡龙成冶金材料有限公司 | A kind of continuous super low carbon steel casting crystallizer protecting residue |
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- 2000-04-30 CN CN 00107260 patent/CN1131118C/en not_active Expired - Fee Related
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| CN1318165C (en) * | 2004-02-27 | 2007-05-30 | 宝山钢铁股份有限公司 | Coverage dregs for ladle |
| CN1321764C (en) * | 2004-06-23 | 2007-06-20 | 青岛斯多伯格三一冶金材料有限公司 | Fluorine free protecting slag for steelmaking and continuous casting and method for manufacturing same |
| CN1788880B (en) * | 2004-12-14 | 2010-08-11 | 上海盘龙实业有限公司 | Dual-functional composite solid protective slag for stainless steel die casting |
| CN100443215C (en) * | 2006-08-25 | 2008-12-17 | 重庆大学 | Protective slag for ultralow carbon steel continuous casting |
| CN101612653B (en) * | 2008-06-23 | 2011-04-13 | 宝山钢铁股份有限公司 | Mold powder for continuous casting of high aluminium-titanium-rare earth steel |
| CN101612652B (en) * | 2008-06-23 | 2011-06-15 | 宝山钢铁股份有限公司 | Mold powder for continuous casting of low nickel and high manganese stainless steel and preparation method thereof |
| CN101637811B (en) * | 2009-08-11 | 2012-06-06 | 河南省西保冶材集团有限公司 | Continuous casting functional protective material specially used for high pressure oil well pipe |
| CN101773996B (en) * | 2010-01-21 | 2012-05-30 | 山西太钢不锈钢股份有限公司 | Continuous casting crystallizer covering slag for non-interstitial atom steel |
| CN103121089A (en) * | 2013-03-12 | 2013-05-29 | 西峡龙成冶金材料有限公司 | Colorful continuous casting crystallizer covering slag for ultra-low carbon steel |
| CN103121089B (en) * | 2013-03-12 | 2014-12-10 | 西峡龙成冶金材料有限公司 | Colorful continuous casting crystallizer covering slag for ultra-low carbon steel |
| CN104511580A (en) * | 2013-09-30 | 2015-04-15 | 上海梅山钢铁股份有限公司 | Molten steel solvent for low-carbon steel |
| CN104399921A (en) * | 2014-11-13 | 2015-03-11 | 北京首钢股份有限公司 | Casting powder |
| CN106694833A (en) * | 2016-12-28 | 2017-05-24 | 西峡龙成冶金材料有限公司 | Crystallizer covering slag special for CSP thin slab continuous casting medium carbon steel |
| CN106513606A (en) * | 2016-12-30 | 2017-03-22 | 西峡龙成冶金材料有限公司 | Continuous casting crystallizer covering slag special for IF steel |
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| CN107282903B (en) * | 2016-12-30 | 2019-04-05 | 西峡龙成冶金材料有限公司 | A kind of continuous super low carbon steel casting crystallizer protecting residue |
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