CN117943516B - Covering slag for solving scale defect of 201 stainless steel wire - Google Patents
Covering slag for solving scale defect of 201 stainless steel wire Download PDFInfo
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- CN117943516B CN117943516B CN202410357212.9A CN202410357212A CN117943516B CN 117943516 B CN117943516 B CN 117943516B CN 202410357212 A CN202410357212 A CN 202410357212A CN 117943516 B CN117943516 B CN 117943516B
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- 238000005406 washing Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/10—Supplying or treating molten metal
- B22D11/11—Treating the molten metal
- B22D11/111—Treating the molten metal by using protecting powders
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Continuous Casting (AREA)
Abstract
The invention relates to the technical field of protective slag, in particular to protective slag for solving the scale defect of a201 stainless steel wire. The composition comprises the following components in percentage by mass: 30-45% of SiO 2, 15-25% of CaO, 4-15% of Al 2O3, 5-18% of MgO, 2-8% of CaF 2, 2-8% of modified Ce 2O3, 2-7% of modifier and 5-12% of modifier, wherein the modified Ce 2O3 is a complex modified product of a mixture of Ce 2O3 and La 2O3 by ethylenediamine tetraacetic acid, and the ratio of Ce 2O3 to La 2O3 is 1:0.4-0.6; the ratio of the ethylenediamine tetraacetic acid to the Ce 2O3 is 0.1-0.3:1. The mixture of Ce 2O3 and La 2O3 is modified by adopting ethylenediamine tetraacetic acid, so that stable complex can be formed with Ce 3+ and La 3+, the utilization rate and the transfer efficiency of rare earth elements in the protective slag are improved, substances containing the modified rare earth elements are more uniformly distributed in the protective slag, and the generation of scale defects of stainless steel wires is effectively inhibited.
Description
Technical Field
The invention relates to the technical field of protective slag, in particular to protective slag for solving the scale defect of a 201 stainless steel wire.
Background
201 Stainless steel has scale-like defects on the surface during the hot working (e.g., hot rolling, continuous casting) stage or during the subsequent cold working. Such defects are expressed as linear or scaly irregular deformation regions, and may be caused by various reasons such as the influence of inclusions in molten steel, stress concentration during processing, poor quality of mold flux, and the like.
When the existing casting powder is applied to the heat treatment of 201 stainless steel, particularly under the high-temperature continuous casting condition, rare earth elements can be difficult to stably exist in the casting powder and effectively migrate into the stainless steel, the effect of the rare earth elements in the microalloying process is affected, the distribution of the elements in the casting powder can be uneven, the rare earth elements cannot be effectively transferred to the surface of molten steel in the continuous casting process, and due to the problems of uneven distribution, low transfer efficiency and the like of the rare earth elements, the effect of the casting powder is poor in the aspects of inhibiting the non-uniformity in the crystallization process and reducing the surface defects, so that the stainless steel wire is easy to suffer from line scale defects.
Disclosure of Invention
The invention aims to provide a covering slag for solving the scale defect of a 201 stainless steel wire, and aims to solve the problems that when the conventional covering slag is applied to the hot working of the 201 stainless steel, rare earth elements are unevenly distributed, the transmission efficiency is low and the like, so that the covering slag has poor effects in inhibiting the non-uniformity in the crystallization process and reducing the surface defect, and the line scale defect of the stainless steel wire is easy to occur.
In order to achieve the purpose, the invention provides the mold flux for solving the scale defect of the 201 stainless steel wire, which comprises the following components in percentage by mass:
SiO2： 30～45％；
CaO： 15～25％；
Al2O3： 4～15％；
MgO： 5～18％；
CaF2： 2～8％；
Modified Ce 2O3: 2-8%;
and (3) a modifier: 2-7%;
And (3) an alterant: 5-12%;
the balance of unavoidable impurities;
Wherein the modified Ce 2O3 is a complex modified product of a mixture of Ce 2O3 and La 2O3 by ethylenediamine tetraacetic acid;
And the ratio of Ce 2O3 to La 2O3 is 1:0.4-0.6;
the ratio of the ethylenediamine tetraacetic acid to the Ce 2O3 is 0.1-0.3:1.
Preferably, the preparation method of the modified Ce 2O3 specifically comprises the following steps:
S1.1, uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.4-0.6, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.1-0.3:1;
S1.2, placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
S1.3, slowly dropwise adding an ethylenediamine tetraacetic acid solution into a Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to perform complexation with the Ce 2O3-La2O3 suspension at a certain reaction temperature and stirring speed, wherein the ethylenediamine tetraacetic acid performs complexation with Ce 3+ and La 3+ ions to generate a reaction product;
S1.4, after the reaction is finished, separating a reaction product from a solution by using a filtering device to obtain a filter cake containing complexing modified Ce 2O3-La2O3, washing the filter cake by using a washing liquid to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally drying the filter cake to obtain complexing modified Ce 2O3 powder.
Preferably, in the step S1.3, the reaction temperature is 60-80 ℃; the complexation of the ethylenediamine tetraacetic acid with Ce 3+ and La 3+ ions is generally carried out in a water bath temperature range from room temperature to a temperature close to the boiling point, because the ethylenediamine tetraacetic acid can be well dissolved at the room temperature and is complexed with metal ions under mild conditions, the reaction temperature is between 60 and 80 ℃ so as to ensure that the dissolution and the complexation reaction of the ethylenediamine tetraacetic acid are smoothly carried out;
The stirring speed is 300-600 rpm to ensure that the solution is uniformly mixed, so that the solid particles are fully dispersed, but excessive foam or solution splashing caused by excessive speed is avoided.
Preferably, in S1.4, the washing liquid is any one of distilled water and deionized water.
Preferably, the modifier is one or a mixture of a Ce-Fe-Si alloy and a La-Fe-Si alloy; the rare earth element is used as a modifier in the steelmaking process, and Ce and La are consistent with ion components in the modified Ce 2O3, so that a better synergistic effect can be formed in a protective slag system, and the improvement of scale defects of the 201 stainless steel wire is promoted together.
The Ce-Fe-Si alloy contains cerium element, and corresponds to Ce3+ ions in modified Ce 2O3, so that the purification and deterioration of the Ce element on molten steel can be enhanced;
the La-Fe-Si alloy can supplement the effect of La element, improve the cleanliness of molten steel and improve the organization structure of the molten steel.
Preferably, the modifier is one or more of ZrO 2、TiO2 and Nd 2O3;
In the casting powder, zrO 2 plays a role of a stabilizer, improves the high temperature resistance and thermal shock resistance of the material, can improve the structure and performance of slag, improves the adsorption capacity and conversion efficiency of slag to nonmetallic inclusions, and is beneficial to reducing the inclusions in metal, thereby improving the quality of stainless steel castings;
Among the mold flux, nd 2O3 is used for refining the slag film, enhancing its ability to adsorb inclusions and prevent secondary oxidation, and contributing to reduction of surface defects of the cast slab such as scale defects;
The modifier is preferably a mixture of ZrO 2 and Nd 2O3.
Preferably, the specific preparation process of the mold flux is as follows:
S8.1, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 30-45% of SiO 2, 15-25% of CaO, 4-15% of Al 2O3, 5-18% of MgO, 2-8% of CaF 2, 2-8% of modified Ce 2O3, 2-7% of modifier and 5-12% of modifier, and uniformly mixing the raw materials of the components:
S8.2, grinding all the raw materials in the pretreated S8.1 into powder, putting into a high-temperature electric furnace, gradually heating to the melting temperature of the raw materials according to a heating curve, and ensuring that the raw materials are fully melted and uniformly mixed;
After the melt is fully melted, keeping the temperature at 1200-1500 ℃ for 3-5h to ensure that all components are fully reacted;
s8.3, adopting a roller way type cooling bed to cool the melt, and controlling the cooling rate of the melt from a molten state to a solid state so as to solidify the melt into a protection slag block;
S8.4, crushing the solidified protective slag blocks into slag particles with required granularity, and screening through a screen to obtain finished protective slag particles; ensuring that the granularity meets the actual requirement in the production process of the 201 stainless steel wire.
Preferably, in S8.2, the temperature rise curve is specifically: gradually heating to 600-800 ℃ at a speed of 5-15 ℃/min, and preserving heat for 1-3 hours to remove water and organic impurities in the raw materials; and then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, and continuously stirring in the process to ensure that the raw materials are uniformly mixed until all the raw materials are completely melted.
Preferably, in S8.3, the cooling rate is specifically: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and then cooling to room temperature at the speed of 5-15 ℃/h, so as to ensure that a stable crystal phase structure is formed in the solidification process of the melt, avoid the problem of overlarge internal stress or uneven components caused by too fast cooling, and finally obtain the protective slag block which has excellent performance and is suitable for solving the problem of scale defect of the 201 stainless steel wire.
Preferably, the granularity of the finished product mold flux particles is 0.35-0.55 mm; the fluidity of the mold flux can be ensured, the uniform covering layer can be formed, the secondary oxidation of the surface of molten steel can be reduced, and the problem of scale-like defects possibly occurring in the 201 stainless steel wire can be reduced.
Compared with the prior art, the invention has the beneficial effects that:
1. In the covering slag for solving the scale defect of the 201 stainless steel wire, the mixture of Ce 2O3 and La 2O3 is modified by adopting ethylenediamine tetraacetic acid, so that a stable complex can be formed with Ce 3+ and La 3+, the utilization rate and the transfer efficiency of rare earth elements in the covering slag are improved, substances containing the modified rare earth elements are more uniformly distributed in the covering slag, and the scaling defect of the stainless steel wire is effectively inhibited.
2. According to the covering slag for solving the scale defect of the 201 stainless steel wire, the activity of Ce 2O3 is enhanced by the modified Ce 2O3, the cerium element can be uniformly dispersed in the covering slag, so that the cerium element is more effectively transferred to the surface of molten steel in the continuous casting process, and the 201 stainless steel is subjected to effective microalloying treatment, so that the surface and internal defects caused by uneven crystallization process can be reduced or eliminated, and the quality of the 201 stainless steel can be improved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) topography of the line scale defect of example 5.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention relates to covering slag for solving the scale defect of a 201 stainless steel wire, which comprises the following components in percentage by mass:
SiO2： 30～45％；
CaO： 15～25％；
Al2O3： 4～15％；
MgO： 5～18％；
CaF2： 2～8％；
Modified Ce 2O3: 2-8%;
and (3) a modifier: 2-7%;
And (3) an alterant: 5-12%;
the balance of unavoidable impurities;
The modified Ce 2O3 is a complex modified product of a mixture of Ce 2O3 and La 2O3 by ethylenediamine tetraacetic acid;
And the ratio of Ce 2O3 to La 2O3 is 1:0.4-0.6;
the ratio of the ethylenediamine tetraacetic acid to the Ce 2O3 is 0.1-0.3:1.
In the embodiments 1-9 and the comparative examples 1-3, the modifier is preferably Ce-Fe-Si alloy, the rare earth element is used as the modifier in the steelmaking process, and Ce is consistent with the ion component in the modified Ce 2O3, so that a better synergistic effect can be formed in a protective slag system, and the improvement of scale defects of the 201 stainless steel wire is promoted together.
The Ce-Fe-Si alloy contains cerium element, and corresponds to Ce3+ ions in modified Ce 2O3, so that the purification and deterioration of the Ce element on molten steel can be enhanced.
The modifier is preferably a mixture of ZrO 2 and Nd 2O3, and in the casting powder, zrO 2 plays a role of a stabilizer, so that the high temperature resistance and the thermal shock resistance of the material are improved, the structure and the performance of slag can be improved, the adsorption capacity and the conversion efficiency of the slag to nonmetallic inclusions are improved, and the reduction of inclusions in metal is facilitated, so that the quality of stainless steel castings is improved;
Among the mold flux, nd 2O3 is used to refine the slag film, enhance its ability to adsorb inclusions and prevent secondary oxidation, and helps to reduce scale defects on the surface of the cast slab.
Example 1
The specific preparation process of the covering slag for solving the scale defect of the 201 stainless steel wire comprises the following steps:
The preparation method of the modified Ce 2O3 specifically comprises the following steps:
uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.4, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.1:1;
Placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
Slowly dripping ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
After the reaction is finished, a filter device is used for separating a reaction product from the solution to obtain a filter cake containing the complexing modification Ce 2O3-La2O3, the filter cake is washed by deionized water to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally, the filter cake is dried to obtain complexing modification Ce 2O3 powder.
Based on the modified Ce 2O3 powder prepared in the step S1, the method is used for preparing the covering slag for solving the scale defect of the 201 stainless steel wire, and the specific preparation process of the covering slag is as follows:
s2, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 40% of SiO 2, 20% of CaO, 5% of Al 2O3, 10% of MgO, 4% of CaF 2, 2% of modified Ce 2O3, 4% of Ce-Fe-Si alloy as a modifier, 7% of a mixture of ZrO 2 and Nd 2O3 as a modifier and the balance of unavoidable impurities, and uniformly mixing the raw materials of the components:
Grinding the raw materials subjected to mixing pretreatment into powder, placing the powder into a high-temperature electric furnace, gradually heating to 600-800 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 1-3 hours to remove water and organic impurities in the raw materials; then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, continuously stirring in the process to ensure that the raw materials are uniformly mixed, gradually heating to the melting temperature of the raw materials until all the raw materials are completely melted, and ensuring that the raw materials are fully melted and uniformly mixed;
after the melt is sufficiently melted, the melt is kept at a high temperature of 1350 ℃ for 5 hours to ensure that the components are sufficiently reacted;
The roller bed type cooling bed is adopted to cool the melt, and the cooling rate of the melt from a molten state to a solid state is controlled, wherein the cooling rate is specifically as follows: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and cooling to room temperature at the speed of 5-15 ℃/h to solidify the melt into a protective slag block;
Crushing the solidified protective slag blocks into slag particles with the required granularity, and sieving the slag particles through a screen to obtain the finished protective slag particles with the granularity of 0.35-0.55 mm.
Example 2
The specific preparation process of the covering slag for solving the scale defect of the 201 stainless steel wire comprises the following steps:
The preparation method of the modified Ce 2O3 specifically comprises the following steps:
Uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.4, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.2:1;
Placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
Slowly dripping ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
After the reaction is finished, a filter device is used for separating a reaction product from the solution to obtain a filter cake containing the complexing modification Ce 2O3-La2O3, the filter cake is washed by deionized water to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally, the filter cake is dried to obtain complexing modification Ce 2O3 powder.
Based on the modified Ce 2O3 powder prepared in the step S1, the method is used for preparing the covering slag for solving the scale defect of the 201 stainless steel wire, and the specific preparation process of the covering slag is as follows:
s2, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 40% of SiO 2, 20% of CaO, 5% of Al 2O3, 10% of MgO, 4% of CaF 2, 2% of modified Ce 2O3, 4% of Ce-Fe-Si alloy as a modifier, 7% of a mixture of ZrO 2 and Nd 2O3 as a modifier and the balance of unavoidable impurities, and uniformly mixing the raw materials of the components:
Grinding the raw materials subjected to mixing pretreatment into powder, placing the powder into a high-temperature electric furnace, gradually heating to 600-800 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 1-3 hours to remove water and organic impurities in the raw materials; then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, continuously stirring in the process to ensure that the raw materials are uniformly mixed, gradually heating to the melting temperature of the raw materials until all the raw materials are completely melted, and ensuring that the raw materials are fully melted and uniformly mixed;
after the melt is sufficiently melted, the melt is kept at a high temperature of 1350 ℃ for 5 hours to ensure that the components are sufficiently reacted;
The roller bed type cooling bed is adopted to cool the melt, and the cooling rate of the melt from a molten state to a solid state is controlled, wherein the cooling rate is specifically as follows: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and cooling to room temperature at the speed of 5-15 ℃/h to solidify the melt into a protective slag block;
Crushing the solidified protective slag blocks into slag particles with the required granularity, and sieving the slag particles through a screen to obtain the finished protective slag particles with the granularity of 0.35-0.55 mm.
Example 3
The specific preparation process of the covering slag for solving the scale defect of the 201 stainless steel wire comprises the following steps:
The preparation method of the modified Ce 2O3 specifically comprises the following steps:
Uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.4, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.3:1;
Placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
Slowly dripping ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
After the reaction is finished, a filter device is used for separating a reaction product from the solution to obtain a filter cake containing the complexing modification Ce 2O3-La2O3, the filter cake is washed by deionized water to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally, the filter cake is dried to obtain complexing modification Ce 2O3 powder.
Based on the modified Ce 2O3 powder prepared in the step S1, the method is used for preparing the covering slag for solving the scale defect of the 201 stainless steel wire, and the specific preparation process of the covering slag is as follows:
s2, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 40% of SiO 2, 20% of CaO, 5% of Al 2O3, 10% of MgO, 4% of CaF 2, 2% of modified Ce 2O3, 4% of Ce-Fe-Si alloy as a modifier, 7% of a mixture of ZrO 2 and Nd 2O3 as a modifier and the balance of unavoidable impurities, and uniformly mixing the raw materials of the components:
Grinding the raw materials subjected to mixing pretreatment into powder, placing the powder into a high-temperature electric furnace, gradually heating to 600-800 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 1-3 hours to remove water and organic impurities in the raw materials; then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, continuously stirring in the process to ensure that the raw materials are uniformly mixed, gradually heating to the melting temperature of the raw materials until all the raw materials are completely melted, and ensuring that the raw materials are fully melted and uniformly mixed;
after the melt is sufficiently melted, the melt is kept at a high temperature of 1350 ℃ for 5 hours to ensure that the components are sufficiently reacted;
The roller bed type cooling bed is adopted to cool the melt, and the cooling rate of the melt from a molten state to a solid state is controlled, wherein the cooling rate is specifically as follows: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and cooling to room temperature at the speed of 5-15 ℃/h to solidify the melt into a protective slag block;
Crushing the solidified protective slag blocks into slag particles with the required granularity, and sieving the slag particles through a screen to obtain the finished protective slag particles with the granularity of 0.35-0.55 mm.
Example 4
The specific preparation process of the covering slag for solving the scale defect of the 201 stainless steel wire comprises the following steps:
The preparation method of the modified Ce 2O3 specifically comprises the following steps:
uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.5, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.1:1;
Placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
Slowly dripping ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
After the reaction is finished, a filter device is used for separating a reaction product from the solution to obtain a filter cake containing the complexing modification Ce 2O3-La2O3, the filter cake is washed by deionized water to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally, the filter cake is dried to obtain complexing modification Ce 2O3 powder.
Based on the modified Ce 2O3 powder prepared in the step S1, the method is used for preparing the covering slag for solving the scale defect of the 201 stainless steel wire, and the specific preparation process of the covering slag is as follows:
s2, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 40% of SiO 2, 20% of CaO, 5% of Al 2O3, 10% of MgO, 4% of CaF 2, 2% of modified Ce 2O3, 4% of Ce-Fe-Si alloy as a modifier, 7% of a mixture of ZrO 2 and Nd 2O3 as a modifier and the balance of unavoidable impurities, and uniformly mixing the raw materials of the components:
Grinding the raw materials subjected to mixing pretreatment into powder, placing the powder into a high-temperature electric furnace, gradually heating to 600-800 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 1-3 hours to remove water and organic impurities in the raw materials; then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, continuously stirring in the process to ensure that the raw materials are uniformly mixed, gradually heating to the melting temperature of the raw materials until all the raw materials are completely melted, and ensuring that the raw materials are fully melted and uniformly mixed;
after the melt is sufficiently melted, the melt is kept at a high temperature of 1350 ℃ for 5 hours to ensure that the components are sufficiently reacted;
The roller bed type cooling bed is adopted to cool the melt, and the cooling rate of the melt from a molten state to a solid state is controlled, wherein the cooling rate is specifically as follows: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and cooling to room temperature at the speed of 5-15 ℃/h to solidify the melt into a protective slag block;
Crushing the solidified protective slag blocks into slag particles with the required granularity, and sieving the slag particles through a screen to obtain the finished protective slag particles with the granularity of 0.35-0.55 mm.
Example 5
The specific preparation process of the covering slag for solving the scale defect of the 201 stainless steel wire comprises the following steps:
The preparation method of the modified Ce 2O3 specifically comprises the following steps:
Uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.5, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.2:1;
Placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
Slowly dripping ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
After the reaction is finished, a filter device is used for separating a reaction product from the solution to obtain a filter cake containing the complexing modification Ce 2O3-La2O3, the filter cake is washed by deionized water to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally, the filter cake is dried to obtain complexing modification Ce 2O3 powder.
Based on the modified Ce 2O3 powder prepared in the step S1, the method is used for preparing the covering slag for solving the scale defect of the 201 stainless steel wire, and the specific preparation process of the covering slag is as follows:
s2, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 40% of SiO 2, 20% of CaO, 5% of Al 2O3, 10% of MgO, 4% of CaF 2, 2% of modified Ce 2O3, 4% of Ce-Fe-Si alloy as a modifier, 7% of a mixture of ZrO 2 and Nd 2O3 as a modifier and the balance of unavoidable impurities, and uniformly mixing the raw materials of the components:
Grinding the raw materials subjected to mixing pretreatment into powder, placing the powder into a high-temperature electric furnace, gradually heating to 600-800 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 1-3 hours to remove water and organic impurities in the raw materials; then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, continuously stirring in the process to ensure that the raw materials are uniformly mixed, gradually heating to the melting temperature of the raw materials until all the raw materials are completely melted, and ensuring that the raw materials are fully melted and uniformly mixed;
after the melt is sufficiently melted, the melt is kept at a high temperature of 1350 ℃ for 5 hours to ensure that the components are sufficiently reacted;
The roller bed type cooling bed is adopted to cool the melt, and the cooling rate of the melt from a molten state to a solid state is controlled, wherein the cooling rate is specifically as follows: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and cooling to room temperature at the speed of 5-15 ℃/h to solidify the melt into a protective slag block;
Crushing the solidified protective slag blocks into slag particles with the required granularity, and sieving the slag particles through a screen to obtain the finished protective slag particles with the granularity of 0.35-0.55 mm.
The mold flux particles prepared in this example were subjected to LF refining to obtain 201 stainless steel, sampling the 201 stainless steel, observing and analyzing inclusions and surface defects by using a Scanning Electron Microscope (SEM), and obtaining inclusion content, surface roughness and line scale distribution of the sample according to the observation and calculation of FIG. 1, with reference to GB/T3280-2015 for stainless steel cold rolled steel sheet and strip, YS/T864-2013 for inspection of surface cleanliness of copper and copper alloy sheet and strip foil, and GB/T5213-2019 for cold rolled low carbon steel sheet and strip.
Example 6
The specific preparation process of the covering slag for solving the scale defect of the 201 stainless steel wire comprises the following steps:
The preparation method of the modified Ce 2O3 specifically comprises the following steps:
uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.5, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.3:1;
Placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
Slowly dripping ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
After the reaction is finished, a filter device is used for separating a reaction product from the solution to obtain a filter cake containing the complexing modification Ce 2O3-La2O3, the filter cake is washed by deionized water to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally, the filter cake is dried to obtain complexing modification Ce 2O3 powder.
Based on the modified Ce 2O3 powder prepared in the step S1, the method is used for preparing the covering slag for solving the scale defect of the 201 stainless steel wire, and the specific preparation process of the covering slag is as follows:
s2, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 40% of SiO 2, 20% of CaO, 5% of Al 2O3, 10% of MgO, 4% of CaF 2, 2% of modified Ce 2O3, 4% of Ce-Fe-Si alloy as a modifier, 7% of a mixture of ZrO 2 and Nd 2O3 as a modifier and the balance of unavoidable impurities, and uniformly mixing the raw materials of the components:
Grinding the raw materials subjected to mixing pretreatment into powder, placing the powder into a high-temperature electric furnace, gradually heating to 600-800 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 1-3 hours to remove water and organic impurities in the raw materials; then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, continuously stirring in the process to ensure that the raw materials are uniformly mixed, gradually heating to the melting temperature of the raw materials until all the raw materials are completely melted, and ensuring that the raw materials are fully melted and uniformly mixed;
after the melt is sufficiently melted, the melt is kept at a high temperature of 1350 ℃ for 5 hours to ensure that the components are sufficiently reacted;
The roller bed type cooling bed is adopted to cool the melt, and the cooling rate of the melt from a molten state to a solid state is controlled, wherein the cooling rate is specifically as follows: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and cooling to room temperature at the speed of 5-15 ℃/h to solidify the melt into a protective slag block;
Crushing the solidified protective slag blocks into slag particles with the required granularity, and sieving the slag particles through a screen to obtain the finished protective slag particles with the granularity of 0.35-0.55 mm.
Example 7
The specific preparation process of the covering slag for solving the scale defect of the 201 stainless steel wire comprises the following steps:
The preparation method of the modified Ce 2O3 specifically comprises the following steps:
Uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.6, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.1:1;
Placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
Slowly dripping ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
After the reaction is finished, a filter device is used for separating a reaction product from the solution to obtain a filter cake containing the complexing modification Ce 2O3-La2O3, the filter cake is washed by deionized water to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally, the filter cake is dried to obtain complexing modification Ce 2O3 powder.
Based on the modified Ce 2O3 powder prepared in the step S1, the method is used for preparing the covering slag for solving the scale defect of the 201 stainless steel wire, and the specific preparation process of the covering slag is as follows:
s2, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 40% of SiO 2, 20% of CaO, 5% of Al 2O3, 10% of MgO, 4% of CaF 2, 2% of modified Ce 2O3, 4% of Ce-Fe-Si alloy as a modifier, 7% of a mixture of ZrO 2 and Nd 2O3 as a modifier and the balance of unavoidable impurities, and uniformly mixing the raw materials of the components:
Grinding the raw materials subjected to mixing pretreatment into powder, placing the powder into a high-temperature electric furnace, gradually heating to 600-800 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 1-3 hours to remove water and organic impurities in the raw materials; then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, continuously stirring in the process to ensure that the raw materials are uniformly mixed, gradually heating to the melting temperature of the raw materials until all the raw materials are completely melted, and ensuring that the raw materials are fully melted and uniformly mixed;
after the melt is sufficiently melted, the melt is kept at a high temperature of 1350 ℃ for 5 hours to ensure that the components are sufficiently reacted;
The roller bed type cooling bed is adopted to cool the melt, and the cooling rate of the melt from a molten state to a solid state is controlled, wherein the cooling rate is specifically as follows: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and cooling to room temperature at the speed of 5-15 ℃/h to solidify the melt into a protective slag block;
Crushing the solidified protective slag blocks into slag particles with the required granularity, and sieving the slag particles through a screen to obtain the finished protective slag particles with the granularity of 0.35-0.55 mm.
Example 8
The specific preparation process of the covering slag for solving the scale defect of the 201 stainless steel wire comprises the following steps:
The preparation method of the modified Ce 2O3 specifically comprises the following steps:
Uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.6, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.2:1;
Placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
Slowly dripping ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
After the reaction is finished, a filter device is used for separating a reaction product from the solution to obtain a filter cake containing the complexing modification Ce 2O3-La2O3, the filter cake is washed by deionized water to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally, the filter cake is dried to obtain complexing modification Ce 2O3 powder.
Based on the modified Ce 2O3 powder prepared in the step S1, the method is used for preparing the covering slag for solving the scale defect of the 201 stainless steel wire, and the specific preparation process of the covering slag is as follows:
s2, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 40% of SiO 2, 20% of CaO, 5% of Al 2O3, 10% of MgO, 4% of CaF 2, 2% of modified Ce 2O3, 4% of Ce-Fe-Si alloy as a modifier, 7% of a mixture of ZrO 2 and Nd 2O3 as a modifier and the balance of unavoidable impurities, and uniformly mixing the raw materials of the components:
Grinding the raw materials subjected to mixing pretreatment into powder, placing the powder into a high-temperature electric furnace, gradually heating to 600-800 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 1-3 hours to remove water and organic impurities in the raw materials; then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, continuously stirring in the process to ensure that the raw materials are uniformly mixed, gradually heating to the melting temperature of the raw materials until all the raw materials are completely melted, and ensuring that the raw materials are fully melted and uniformly mixed;
after the melt is sufficiently melted, the melt is kept at a high temperature of 1350 ℃ for 5 hours to ensure that the components are sufficiently reacted;
The roller bed type cooling bed is adopted to cool the melt, and the cooling rate of the melt from a molten state to a solid state is controlled, wherein the cooling rate is specifically as follows: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and cooling to room temperature at the speed of 5-15 ℃/h to solidify the melt into a protective slag block;
Crushing the solidified protective slag blocks into slag particles with the required granularity, and sieving the slag particles through a screen to obtain the finished protective slag particles with the granularity of 0.35-0.55 mm.
Example 9
The specific preparation process of the covering slag for solving the scale defect of the 201 stainless steel wire comprises the following steps:
The preparation method of the modified Ce 2O3 specifically comprises the following steps:
Uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.6, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.3:1;
Placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
Slowly dripping ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
After the reaction is finished, a filter device is used for separating a reaction product from the solution to obtain a filter cake containing the complexing modification Ce 2O3-La2O3, the filter cake is washed by deionized water to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally, the filter cake is dried to obtain complexing modification Ce 2O3 powder.
Based on the modified Ce 2O3 powder prepared in the step S1, the method is used for preparing the covering slag for solving the scale defect of the 201 stainless steel wire, and the specific preparation process of the covering slag is as follows:
s2, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 40% of SiO 2, 20% of CaO, 5% of Al 2O3, 10% of MgO, 4% of CaF 2, 2% of modified Ce 2O3, 4% of Ce-Fe-Si alloy as a modifier, 7% of a mixture of ZrO 2 and Nd 2O3 as a modifier and the balance of unavoidable impurities, and uniformly mixing the raw materials of the components:
Grinding the raw materials subjected to mixing pretreatment into powder, placing the powder into a high-temperature electric furnace, gradually heating to 600-800 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 1-3 hours to remove water and organic impurities in the raw materials; then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, continuously stirring in the process to ensure that the raw materials are uniformly mixed, gradually heating to the melting temperature of the raw materials until all the raw materials are completely melted, and ensuring that the raw materials are fully melted and uniformly mixed;
after the melt is sufficiently melted, the melt is kept at a high temperature of 1350 ℃ for 5 hours to ensure that the components are sufficiently reacted;
The roller bed type cooling bed is adopted to cool the melt, and the cooling rate of the melt from a molten state to a solid state is controlled, wherein the cooling rate is specifically as follows: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and cooling to room temperature at the speed of 5-15 ℃/h to solidify the melt into a protective slag block;
Crushing the solidified protective slag blocks into slag particles with the required granularity, and sieving the slag particles through a screen to obtain the finished protective slag particles with the granularity of 0.35-0.55 mm.
Example 10
The specific preparation process of the covering slag for solving the scale defect of the 201 stainless steel wire comprises the following steps:
The preparation method of the modified Ce 2O3 specifically comprises the following steps:
Uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.5, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.2:1;
Placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
Slowly dripping ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
After the reaction is finished, a filter device is used for separating a reaction product from the solution to obtain a filter cake containing the complexing modification Ce 2O3-La2O3, the filter cake is washed by deionized water to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally, the filter cake is dried to obtain complexing modification Ce 2O3 powder.
Based on the modified Ce 2O3 powder prepared in the step S1, the method is used for preparing the covering slag for solving the scale defect of the 201 stainless steel wire, and the specific preparation process of the covering slag is as follows:
S2, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 40% of SiO 2, 20% of CaO, 5% of Al 2O3, 10% of MgO, 4% of CaF 2, 5% of modified Ce 2O3, 4% of Ce-Fe-Si alloy as a modifier, 7% of a mixture of ZrO 2 and Nd 2O3 as a modifier and the balance of unavoidable impurities, and uniformly mixing the raw materials of the components:
Grinding the raw materials subjected to mixing pretreatment into powder, placing the powder into a high-temperature electric furnace, gradually heating to 600-800 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 1-3 hours to remove water and organic impurities in the raw materials; then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, continuously stirring in the process to ensure that the raw materials are uniformly mixed, gradually heating to the melting temperature of the raw materials until all the raw materials are completely melted, and ensuring that the raw materials are fully melted and uniformly mixed;
after the melt is sufficiently melted, the melt is kept at a high temperature of 1350 ℃ for 5 hours to ensure that the components are sufficiently reacted;
The roller bed type cooling bed is adopted to cool the melt, and the cooling rate of the melt from a molten state to a solid state is controlled, wherein the cooling rate is specifically as follows: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and cooling to room temperature at the speed of 5-15 ℃/h to solidify the melt into a protective slag block;
Crushing the solidified protective slag blocks into slag particles with the required granularity, and sieving the slag particles through a screen to obtain the finished protective slag particles with the granularity of 0.35-0.55 mm.
Example 11
The specific preparation process of the covering slag for solving the scale defect of the 201 stainless steel wire comprises the following steps:
The preparation method of the modified Ce 2O3 specifically comprises the following steps:
Uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.5, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.2:1;
Placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
Slowly dripping ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
After the reaction is finished, a filter device is used for separating a reaction product from the solution to obtain a filter cake containing the complexing modification Ce 2O3-La2O3, the filter cake is washed by deionized water to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally, the filter cake is dried to obtain complexing modification Ce 2O3 powder.
Based on the modified Ce 2O3 powder prepared in the step S1, the method is used for preparing the covering slag for solving the scale defect of the 201 stainless steel wire, and the specific preparation process of the covering slag is as follows:
S2, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 40% of SiO 2, 20% of CaO, 5% of Al 2O3, 10% of MgO, 4% of CaF 2, 8% of modified Ce 2O3, 4% of Ce-Fe-Si alloy as a modifier, 7% of a mixture of ZrO 2 and Nd 2O3 as a modifier and the balance of unavoidable impurities, and uniformly mixing the raw materials of the components:
Grinding the raw materials subjected to mixing pretreatment into powder, placing the powder into a high-temperature electric furnace, gradually heating to 600-800 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 1-3 hours to remove water and organic impurities in the raw materials; then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, continuously stirring in the process to ensure that the raw materials are uniformly mixed, gradually heating to the melting temperature of the raw materials until all the raw materials are completely melted, and ensuring that the raw materials are fully melted and uniformly mixed;
after the melt is sufficiently melted, the melt is kept at a high temperature of 1350 ℃ for 5 hours to ensure that the components are sufficiently reacted;
The roller bed type cooling bed is adopted to cool the melt, and the cooling rate of the melt from a molten state to a solid state is controlled, wherein the cooling rate is specifically as follows: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and cooling to room temperature at the speed of 5-15 ℃/h to solidify the melt into a protective slag block;
Crushing the solidified protective slag blocks into slag particles with the required granularity, and sieving the slag particles through a screen to obtain the finished protective slag particles with the granularity of 0.35-0.55 mm.
Comparative example 1
Unmodified Ce 2O3 was used by the method of example 5.
Comparative example 2
The procedure of example 5 was employed, differing from example 5 in that La 2O3 was not used in the Ce 2O3 modification.
Comparative example 3
The procedure of example 5 was used, differing from example 5 in that ethylenediamine tetraacetic acid was not used in the Ce 2O3 modification.
The mold flux prepared by the above examples 1 to 11 and comparative examples 1 to 3 had the following performance test methods: refer to GB/T3280-2015, YS/T864-2013, copper and copper alloy sheet and strip foil surface cleanliness inspection method, and GB/T5213-2019, cold rolled low carbon Steel sheet and strip; molten steel smelting is carried out by using an induction furnace, a ladle and a tundish are configured, LF refining is carried out, and a Scanning Electron Microscope (SEM) is used for observing and analyzing inclusions and surface defects, as shown in FIG. 1 in detail;
wherein, in LF refining process, adding the protective slag to be tested, and adjusting the alkalinity of the slag to 1.5-1.8; expanding the tundish volume to 45t to ensure sufficient time for refining; strictly executing protective casting measures to prevent oxidation caused by contact of molten steel and air; sampling from different positions to conduct macroscopic and microscopic analysis after casting is completed; performing macro morphology observation on the sampled 201 stainless steel, and recording surface defect conditions to obtain data indexes of inclusion content, surface roughness and linear scale distribution respectively;
the content of the inclusions is represented by the ratio of the total area occupied by the inclusions to the total area of the observation area, and the inclusions are sampled and evaluated based on the standard of GB/T10561-2023 microscopic inspection of the content of nonmetallic inclusions in steel.
The surface roughness is represented by average roughness (Rq), representing the square root of the average of the square values of the deviation of points on the surface profile from the center line;
The linear scale distribution is represented by linear scale distribution density, and represents the number of linear scales in a unit area, and reflects the density degree of the linear scales;
Based on the performance data of the mold flux obtained by the above experiments, the effect of the mold flux on reducing the line scale defect was evaluated, and the performance data of the 201 stainless steel prepared from the mold fluxes of examples 1 to 11 and comparative examples 1 to 3 described above are shown in table 1:
TABLE 1 Performance data for the 201 stainless steels of examples 1-11 and comparative examples 1-3
The above data fully show the performance data of examples 1-11 compared to the 201 stainless steel of comparative examples 1-3, and according to the above data, the specific analysis is as follows:
It can be seen from examples 1 to 3, examples 4 to 6 and examples 7 to 9 that: as the content of the ethylenediamine tetraacetic acid in the modified Ce 2O3 is increased, the inclusion content, the average roughness and the linear scale distribution density of the 201 stainless steel are all reduced, and as can be seen by comparing with comparative example 3, when the ethylenediamine tetraacetic acid in the modified Ce 2O3 is removed, the inclusion content, the average roughness and the linear scale distribution density of the 201 stainless steel are all obviously increased, so that the ethylenediamine tetraacetic acid can enhance the modification effect of the Ce 2O3, and meanwhile, the effect of the ethylenediamine tetraacetic acid in the 201 stainless steel wire protective slag is optimized, so that the scale defect of the stainless steel wire is more effectively prevented and reduced;
The ethylenediamine tetraacetic acid has strong complexing ability with the rare earth elements Ce 3+ and La 3+, and increasing the content of the ethylenediamine tetraacetic acid means that more opportunities are provided for forming stable complexes with Ce 2O3 and La 2O3, which is helpful for improving the utilization rate and the transfer efficiency of the rare earth elements in the subsequent procedures, and meanwhile, the complexes formed by the ethylenediamine tetraacetic acid, ce 2O3 and La 2O3 have better water solubility and dispersibility, so that substances containing modified rare earth elements can be more uniformly distributed in the whole casting powder system in the process of preparing the casting powder, thereby ensuring the uniform effect on the stainless steel surface in the continuous casting process and being helpful for reducing the linear scale defects.
Further, comparative examples 1, 4 and 7, respectively; comparative examples 2, 5 and 8; comparative examples 3, 6 and 9 can be seen: as the La 2O3 content in the modified Ce 2O3 is increased, the inclusion content, the average roughness and the linear scale distribution density of the 201 stainless steel are all reduced, and as can be seen by comparing with comparative example 2, when La 2O3 in the modified Ce 2O3 is removed, the inclusion content, the average roughness and the linear scale distribution density of the 201 stainless steel are all obviously increased, so that La 2O3 can also enhance the modification effect of Ce 2O3, and simultaneously optimize the effect of the La 2O3 in the 201 stainless steel wire protective slag, so that the scale defect of the stainless steel wire is more effectively prevented and reduced;
The La element in La 2O3 has the capability of refining grains and improving a metal structure, the content of La 2O3 is increased, la element can be more effectively introduced into the stainless steel, and the mechanical property and corrosion resistance of the stainless steel are improved through microalloying; meanwhile, la 2O3 is used for improving the dispersibility of Ce 2O3 in a casting powder matrix, avoiding agglomeration, improving the uniform distribution of modified Ce 2O3 in the casting powder, thereby enhancing the protection effect and the modification effect of the modified Ce 2O3 on the stainless steel surface in the continuous casting process, and the combination of La 2O3 and Ce 2O3 can realize a synergistic effect, so that the overall performance of the modified material is improved, la 2O3 and Ce 2O3 are both rare earth oxides, have similar electronic structures and physical and chemical properties, can complement each other after combination, and enhance the respective activities in the aspects of catalysis, reduction, antioxidation and the like;
Further, la 2O3 can adjust the melting point, viscosity, surface tension and other physical properties of slag, and when the slag is compositely modified with Ce 2O3, the fluidity, wettability and spreadability of the slag at high temperature can be optimized, so that a stable protective layer with good isolation effect can be formed, and scale defects possibly occurring in the continuous casting process of the 201 stainless steel wire can be remarkably reduced.
Still further, considering example 5 as the most preferred example, it can be seen by comparing example 5, example 10 and example 11: along with the gradual increase of the content of the modified Ce 2O3 in the preparation of the covering slag for solving the scale defect of the 201 stainless steel wire, the inclusion content, the average roughness and the scale distribution density of the 201 stainless steel wire are obviously reduced, and the effect of the modified Ce 2O3 on the inclusion content, the average roughness and the scale distribution density of the 201 stainless steel wire is obvious as shown by combining with comparative example 1;
The activity of Ce 2O3 in the modified Ce 2O3 is enhanced, and the modified Ce 2O3 can be uniformly dispersed in the casting powder, so that cerium element is more effectively transferred to the surface of molten steel in the continuous casting process, and the 201 stainless steel is subjected to effective microalloying treatment, thereby being beneficial to reducing or eliminating surface and internal defects caused by non-uniformity in the crystallization process and improving the quality of the 201 stainless steel;
Ce 2O3 can adsorb and capture oxygen and other harmful impurities in molten steel, reduce the oxidation degree of the molten steel, thereby reducing surface defects caused by oxidation, such as scale-like defects, cracks, inclusions and the like, and the modified Ce 2O3 can also improve the wettability and lubricity of the covering slag, reduce the friction resistance between the molten steel and the wall of the crystallizer in the crystallizer, and further reduce the mechanical scratches and crack formation on the surface of a casting blank; not only enhances the basic functions of the mold flux, namely, prevents oxidation and air suction, but also improves the surface quality and the internal quality of the 201 stainless steel in the continuous casting process;
it is worth noting that the ethylenediamine tetraacetic acid has strong complexing ability with Ce 3+ and La 3+, can form stable complex with Ce 2O3 and La 2O3, and the formation of the complex helps the rare earth element to be transferred more uniformly in molten steel, because the complex is more flowable and dispersible than free rare earth oxide, the solubility and stability of the rare earth element in subsequent procedures are increased, so that the Ce and La are more easily and uniformly dispersed in a mold flux system, the EDTA can disperse the rare earth element in the mold flux in the form of smaller particles, and such tiny particles are more easily absorbed by the molten steel, thereby promoting the rare earth microalloying in stainless steel; without the assistance of ethylenediamine tetraacetic acid, rare earth elements may exist in a lower solubility, which leads to uneven distribution in the mold flux and is unfavorable for the effective action on the stainless steel surface in the continuous casting process;
Meanwhile, the complex formed by the ethylenediamine tetraacetic acid, the Ce 2O3 and the La 2O3 has better water solubility and dispersibility, and is beneficial to more uniformly distributing substances containing modified rare earth elements in the process of preparing the covering slag; the uniformly distributed modified material can ensure the uniform effect on the stainless steel surface in the continuous casting process, and effectively reduce the linear scale defect; if no ethylenediamine tetraacetic acid participates, ce 2O3 and La 2O3 are locally aggregated due to poor dispersibility, so that the action effect of the Ce 2O3 and La in the covering slag is affected;
and the introduction and the distribution of Ce and La in the stainless steel are promoted by complexation of the ethylenediamine tetraacetic acid, so that the mechanical property and the corrosion resistance of the stainless steel are improved by microalloying. The distribution of Ce and La in the stainless steel is possibly uneven without ethylenediamine tetraacetic acid, so that the microalloying effect is weakened, and the quality of the stainless steel is not improved;
Therefore, although the ethylene diamine tetraacetic acid does not directly participate in the improvement of the quality of the covering slag, the ethylene diamine tetraacetic acid promotes the utilization rate, the transmission efficiency and the dispersibility of the rare earth element by forming a complex with Ce 2O3 and La 2O3, and promotes the microalloying effect of the rare earth element in the stainless steel, thereby indirectly but obviously optimizing the performance of the covering slag and effectively preventing and reducing the scale defect of the stainless steel wire; therefore, the direct addition of Ce 2O3 and La 2O3 alone cannot achieve the same modification effect and mold flux quality improvement effect as the addition of ethylenediamine tetraacetic acid.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are only preferred embodiments of the present invention, and are not intended to limit the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The covering slag for solving the scale defect of the 201 stainless steel wire is characterized by comprising the following components in percentage by mass:
SiO2： 30～45％；
CaO： 15～25％；
Al2O3： 4～15％；
MgO： 5～18％；
CaF2： 2～8％；
Modified Ce 2O3: 2-8%;
and (3) a modifier: 2-7%;
And (3) an alterant: 5-12%;
the balance of unavoidable impurities;
Wherein the modified Ce 2O3 is a complex modified product of a mixture of Ce 2O3 and La 2O3 by ethylenediamine tetraacetic acid;
And the ratio of Ce 2O3 to La 2O3 is 1:0.4-0.6;
the ratio of the ethylenediamine tetraacetic acid to the Ce 2O3 is 0.1-0.3:1.
2. The covering slag for solving the scale defect of 201 stainless steel wires according to claim 1, wherein the preparation method of the modified Ce 2O3 is specifically as follows:
S1.1, uniformly mixing Ce 2O3 and La 2O3 powder according to the mass ratio of 1:0.4-0.6, and preparing ethylenediamine tetraacetic acid according to the mass ratio of ethylenediamine tetraacetic acid to Ce 2O3 of 0.1-0.3:1;
S1.2, placing the mixed Ce 2O3-La2O3 powder into deionized water, and uniformly dispersing under the stirring condition to obtain Ce 2O3-La2O3 suspension;
S1.3, slowly dropwise adding an ethylenediamine tetraacetic acid solution into the Ce 2O3-La2O3 suspension, and keeping the Ce 2O3-La2O3 suspension to carry out complexation on the ethylenediamine tetraacetic acid and the Ce 2O3-La2O3 suspension under the conditions of stirring speed of 300-600 rpm and reaction temperature of 60-80 ℃ to generate a reaction product;
S1.4, after the reaction is finished, separating a reaction product from a solution by using a filtering device to obtain a filter cake containing complexing modified Ce 2O3-La2O3, washing the filter cake by using a washing liquid to remove unreacted ethylenediamine tetraacetic acid and other byproducts, and finally drying the filter cake to obtain complexing modified Ce 2O3 powder.
3. The mold flux for solving the scale defect of 201 stainless steel wire according to claim 2, wherein in S1.4, the washing liquid is any one of distilled water and deionized water.
4. The covering slag for solving the scale defect of 201 stainless steel wire according to claim 1, wherein the modifier is one or more of a Ce-Fe-Si alloy and a La-Fe-Si alloy.
5. The covering slag for solving the scale defect of 201 stainless steel wire according to claim 1, wherein said modifier is one or more of the mixture of ZrO 2、TiO2 and Nd 2O3.
6. The mold flux for solving the scale defect of 201 stainless steel wire according to claim 1, wherein the specific preparation process of the mold flux is as follows:
S8.1, respectively weighing the following raw material components in percentage by mass according to the content requirements of each component in the mold flux formula: 30-45% of SiO 2, 15-25% of CaO, 4-15% of Al 2O3, 5-18% of MgO, 2-8% of CaF 2, 2-8% of modified Ce 2O3, 2-7% of modifier and 5-12% of modifier, and uniformly mixing the raw materials of the components:
s8.2, grinding all the raw materials in the step S8.1 after being uniformly mixed into powder, and putting the powder into a high-temperature electric furnace, and gradually heating to the melting temperature of the raw materials according to a heating curve;
After the melt is fully melted, keeping the temperature at 1200-1500 ℃ for 3-5h to ensure that all components are fully reacted;
s8.3, adopting a roller way type cooling bed to cool the melt, and controlling the cooling rate of the melt from a molten state to a solid state so as to solidify the melt into a protection slag block;
S8.4, crushing the solidified protective slag blocks into slag particles with required granularity, and screening through a screen to obtain the finished protective slag particles.
7. The covering slag for solving the scale defect of the 201 stainless steel wire according to claim 6, wherein in S8.2, the heating curve is specifically: gradually heating to 600-800 ℃ at a speed of 5-15 ℃/min, and preserving heat for 1-3 hours to remove water and organic impurities in the raw materials; and then continuously heating to 1200-1500 ℃ at the speed of 2-8 ℃/min, and continuously stirring in the process to ensure that the raw materials are uniformly mixed until all the raw materials are completely melted.
8. The mold flux for solving the scale defect of 201 stainless steel wire according to claim 6, wherein in S8.3, the cooling rate is specifically: slowly cooling to 800-1000 ℃ at the speed of 10-30 ℃/h, and then cooling to room temperature at the speed of 5-15 ℃/h.
9. The mold flux for solving the scale defect of 201 stainless steel wire according to claim 6, wherein the particle size of the finished mold flux particles is 0.35-0.55 mm.
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