阅读说明：本技术 用于冶炼含Ce的Fe-Ni软磁合金的渣系及其使用方法 (Slag system for smelting Ce-containing Fe-Ni soft magnetic alloy and use method thereof ) 是由 董艳伍 姚科安 姜周华 李毓硕 杜书扬 于 2020-10-30 设计创作，主要内容包括：用于冶炼含Ce的Fe-Ni软磁合金的渣系及其使用方法,成分按质量百分比含CaO 15～27％,Al_2O_3 10～22％,NaF 4～6％,MoO_2 0～2％,MgO 3～5％,CeO_2 3～15％,SiO_2 1～2％,余量为CaF_2；方法为：(1)将用于冶炼含Ce的Fe-Ni软磁合金的渣系在1450±5℃预熔,然后破碎；(2)预熔渣块料600±5℃烘烤制成预熔渣；(3)在引锭板上铺设合金屑,在合金屑与结晶器内壁之间的空间铺设萤石粉；(4)在氩气气氛条件下,下降自耗电极进行引弧,将预熔渣加入结晶器内进行化渣；(5)化渣完成后形成渣池并进行电渣重熔冶炼。本发明的渣系可以解决电渣重熔冶炼含稀土Ce的Fe-Ni合金过程中发生的Ce、Mo等元素烧损问题,制备的含Ce的Fe-Ni软磁合金成分质量良好,元素分布均匀。(The slag system for smelting Ce-containing Fe-Ni soft magnetic alloy comprises, by mass, 15-27% of CaO and Al 2 O 3 10～22％，NaF 4～6％，MoO 2 0～2％，MgO 3～5％，CeO 2 3～15％，SiO 2 1-2% and the balance of CaF 2 (ii) a The method comprises the following steps: (1) will be used for smelting C-containinge, pre-melting the slag system of the Fe-Ni soft magnetic alloy at 1450 +/-5 ℃, and then crushing; (2) baking the pre-melted slag lump material at 600 +/-5 ℃ to prepare pre-melted slag; (3) alloy scraps are laid on the dummy plate, and fluorite powder is laid in the space between the alloy scraps and the inner wall of the crystallizer; (4) under the condition of argon atmosphere, a consumable electrode is lowered to perform arc striking, and pre-melted slag is added into a crystallizer to perform slag melting; (5) and forming a slag pool after slagging is finished and carrying out electroslag remelting smelting. The slag system can solve the problem of burning loss of elements such as Ce, Mo and the like in the process of electroslag remelting smelting of Fe-Ni alloy containing rare earth Ce, and the prepared Fe-Ni soft magnetic alloy containing Ce has good component quality and uniform element distribution.)

1. For smelting ofThe slag system of the Fe-Ni soft magnetic alloy of Ce is characterized in that the components contain 15-27% of CaO and Al according to the mass percentage₂O₃ 10～22％，NaF 4～6％，MoO₂ 0～2％，MgO 3～5％，CeO₂ 3～15％，SiO₂1-2% and the balance of CaF₂。

2. The slag system for smelting Fe-Ni soft magnetic alloy containing Ce according to claim 1, characterized in that its melting temperature is 1200-1300 ℃.

3. The slag system for smelting a Ce-containing Fe-Ni soft magnetic alloy according to claim 1, characterized in that it has an electrical resistivity of 0.382 to 0.578 Ω -cm at 1550 ± 5 ℃.

4. The slag system for smelting a Ce-containing Fe-Ni soft magnetic alloy according to claim 1, characterized in that its viscosity at 1550 ± 5 ℃ is 0.015-0.027 Pa-s.

5. Use of the slag system for smelting Ce-containing Fe-Ni soft magnetic alloys according to claim 1, characterized by comprising the steps of:

(1) pre-melting the slag system for smelting the Ce-containing Fe-Ni soft magnetic alloy at 1450 +/-5 ℃ for at least 15min, and then air-cooling to room temperature and crushing to prepare pre-melted slag blocks;

(2) heating the pre-melted slag lump material to 600 +/-5 ℃, baking for 3-6 h, and cooling to room temperature along with the furnace to prepare pre-melted slag;

(3) alloy scraps are laid on the dummy bar plate, the alloy scraps are positioned at the projection of the consumable electrode on the dummy bar plate, and the laying thickness of the alloy scraps is 30-50 mm; meanwhile, fluorite powder is laid in the space between the alloy scraps and the inner wall of the crystallizer, and the laying thickness of the fluorite powder is 5-10 mm; the alloy scrap has the same components as the consumable electrode;

(4) under the condition of argon atmosphere, a consumable electrode is lowered to perform arc striking, and after the arc striking is finished, pre-melted slag is added into a crystallizer to perform slag melting; the consumable electrode is Fe-Ni soft magnetic alloy containing Ce, and comprises 13-50% of Fe, 0-7% of Mo, 0.1-1% of Si, 0.1-1% of Mn, 0.001-0.06% of Ce, and the balance of Ni and unavoidable impurities by mass percent;

(5) and forming a slag pool after slagging is finished, carrying out electroslag remelting, and adding aluminum particles into the slag pool in the electroslag remelting process until electroslag remelting is finished.

6. The use method of the slag system for smelting Fe-Ni soft magnetic alloy containing Ce according to claim 5, characterized in that in the step (4), the calculation formula of the amount of pre-melted slag added into the crystallizer is (650-1250) xD³kg, wherein D is the internal diameter of the crystallizer in m.

7. The use method of the slag system for smelting Fe-Ni soft magnetic alloy containing Ce according to claim 5, characterized in that in the step (5), aluminum particles are added every 3-5 min; the adding amount of the aluminum particles is 0.1-0.2% of the mass of the consumable electrode melted within 3-5 min.

8. The use of the slag system for smelting Ce-containing Fe-Ni soft magnetic alloy according to claim 5, wherein in step (4), the unavoidable impurities contain N < 0.001%, Al < 0.03%, S < 0.004%, and O < 0.002% by weight.

Technical Field

The invention belongs to the technical field of metallurgy, and particularly relates to a slag system for smelting Fe-Ni soft magnetic alloy containing Ce and a using method thereof.

Background

The soft magnetic material is a magnetic material with high magnetic permeability and small demagnetization factor, can be quickly magnetized in a weak magnetic field, and has high demagnetization speed after an external magnetic field is cancelled, so that the coercive force and remanence are far lower than those of rare earth permanent magnets and ferromagnets. The soft magnetic alloy has various varieties and wide application range, and is particularly applied to the fields of magnetic recording, magnetic shielding, transformers and the like, so that other magnetic materials cannot be replaced; Fe-Ni soft magnetic alloys are one of the commonly used soft magnetic materials.

The factors influencing the magnetic performance of the soft magnetic alloy are mainly as follows: chemical components, smelting process, alloy cleanliness, heat treatment process and the like. Improving the purity of the alloy, modifying harmful impurities in the alloy and improving the alloy structure, and is an effective means for improving the soft magnetic performance of the alloy.

Rare earth Ce is an alloy additive commonly used in the metallurgical industry, and during the smelting process, the rare earth Ce is easy to react with harmful impurity elements in alloy liquid to generate inclusions with small density and high melting point, and the inclusions are discharged from the metal liquid, and meanwhile, the mass fractions of oxygen and sulfur in steel can be deeply reduced, and the segregation of the harmful elements in grain boundaries can be reduced. In addition, the addition of Ce can also change the alloy structure and adjust the grain size of the alloy.

The smelting process for producing Fe-Ni alloy at the present stage is vacuum induction smelting, but the vacuum induction smelting has almost no removal capacity for impurity elements, and crucible materials are easily brought into the smelting process, so that new pollution is caused; in addition, the alloy smelted by vacuum induction smelting has poor surface quality, more processing treatment is needed, and more waste is generated on the material.

The electroslag remelting ingot has the characteristics of uniform components, high purity, compact structure and the like, so the electroslag remelting is an important smelting means of high-temperature alloy; compared with the vacuum induction melting process, the electroslag remelting equipment is simple, the production cost is low, the operation is convenient, the surface of the cast ingot is smooth and clean, the thermoplasticity is good, and the yield is high. In the field of smelting nickel-based alloys, electroslag remelting has become a more interesting smelting process. However, the Fe-Ni soft magnetic alloy containing rare earth Ce has a certain problem in smelting, namely the burning loss of Ce element and other easily-oxidized elements in the alloy after electroslag remelting secondary refining, so that a new electroslag remelting process needs to be developed to solve the problem.

Disclosure of Invention

The invention aims to provide a slag system for smelting Fe-Ni soft magnetic alloy containing Ce and a using method thereof₂、MoO₂The problem of burning loss of Ce and Mo is solved, and NaF is added to adjust physical parameters of the slag system, so that the negative influence of the antioxidant component is counteracted.

The slag system for smelting the Ce-containing Fe-Ni soft magnetic alloy comprises, by mass, 15-27% of CaO and Al₂O₃ 10～22％，NaF 4～6％，MoO₂ 0～2％，MgO 3～5％，CeO₂ 3～15％，SiO₂1-2% and the balance of CaF₂。

The melting temperature of the slag system for smelting the Ce-containing Fe-Ni soft magnetic alloy is 1200-1300 ℃.

The resistivity of the slag system for smelting the Fe-Ni soft magnetic alloy containing Ce at 1550 +/-5 ℃ is 0.382-0.578 omega-cm.

The viscosity of the slag system for smelting the Ce-containing Fe-Ni soft magnetic alloy at 1550 +/-5 ℃ is 0.015-0.027 Pa.s.

The use method of the slag system for smelting the Ce-containing Fe-Ni soft magnetic alloy comprises the following steps:

1. pre-melting the slag system for smelting the Ce-containing Fe-Ni soft magnetic alloy at 1450 +/-5 ℃ for at least 15min, and then air-cooling to room temperature and crushing to prepare pre-melted slag blocks;

2. heating the pre-melted slag lump material to 600 +/-5 ℃, baking for 3-6 h, and cooling to room temperature along with the furnace to prepare pre-melted slag;

3. alloy scraps are laid on the dummy bar plate, the alloy scraps are positioned at the projection of the consumable electrode on the dummy bar plate, and the laying thickness of the alloy scraps is 30-50 mm; meanwhile, fluorite powder is laid in the space between the alloy scraps and the inner wall of the crystallizer, and the laying thickness of the fluorite powder is 5-10 mm; the alloy scrap has the same components as the consumable electrode;

4. under the condition of argon atmosphere, a consumable electrode is lowered to perform arc striking, and after the arc striking is finished, pre-melted slag is added into a crystallizer to perform slag melting; the consumable electrode is Fe-Ni soft magnetic alloy containing Ce, and comprises 13-50% of Fe, 0-7% of Mo, 0.1-1% of Si, 0.1-1% of Mn, 0.001-0.06% of Ce, and the balance of Ni and unavoidable impurities by mass percent;

5. and forming a slag pool after slagging is finished, carrying out electroslag remelting, and adding aluminum particles into the slag pool in the electroslag remelting process until electroslag remelting is finished.

In the step 4, the calculation formula of the amount of the premelting slag added into the crystallizer is (650-1250) multiplied by D³kg, wherein D is the internal diameter of the crystallizer in m.

In the step 5, adding the aluminum particles once every 3-5 min; the adding amount of the aluminum particles is 0.1-0.2% of the mass of the consumable electrode melted within 3-5 min.

In the step 4, the unavoidable impurities comprise, by weight, less than 0.001% of N, less than 0.03% of Al, less than 0.004% of S and less than 0.002% of O.

For electroslag remelting Fe-Ni alloy containing smelting rare earth Ce, the oxidation reaction of Mo and Ce can occur in the smelting process, and the thermodynamic calculation finds that MgO and MoO exist in the slag₂、CeO₂The reaction can be inhibited, and the oxidation can be inhibited by adding a proper amount of Al in the smelting process; adding CeO into the slag system₂3-15%, and reducing the burning loss of the Ce element; in electroslag remeltingIn the process, a layer of protective film can be formed on the surface of the slag pool by adding a proper amount of MgO into the slag, and the air suction capacity of the slag pool in the smelting process is reduced, so that the oxygen absorption of the slag pool is reduced, the oxygen transfer of the slag pool to a metal molten pool is reduced, and the content of hydrogen in the cast ingot can be reduced; therefore, 4-6% of MgO is added; as the slag system is added with MgO and MoO with high melting point₂、CeO₂The melting point and the viscosity of the slag system are increased, but the melting point and the viscosity of the slag system are required to be in proper ranges by electroslag remelting smelting, so that the part of CaF is replaced by NaF with low melting point and low viscosity₂Adjusting the physical parameters of the slag system, and adding 5-7% NaF.

The slag system is used for solving the problem of oxidation of easily-oxidized elements in the electroslag remelting process; the slag system used by the electroslag remelting requirement has appropriate physical parameters, wherein the melting temperature and viscosity of the slag system are the main factors for judging whether the slag system is suitable for alloy smelting, and after an antioxidant component is added into the slag system, the melting temperature and viscosity of the slag system are increased, so that NaF is added to adjust the physical parameters of the slag system; in the electroslag remelting smelting process, oxygen absorption of a slag pool is one of the reasons for increasing the oxygen content in a cast ingot after smelting and burning loss of easily-oxidized elements, so that adding aluminum particles into the slag pool in the smelting process is an excellent method for inhibiting the burning loss of the easily-oxidized elements in the alloy; the method can solve the problem of burning loss of elements such as Ce, Mo and the like in the process of electroslag remelting smelting of the Fe-Ni alloy containing rare earth Ce, and the prepared Fe-Ni soft magnetic alloy containing Ce has good component quality and uniform element distribution.

Detailed Description

The alloy scraps in the embodiment of the invention are cleaned by 5% hydrochloric acid alcohol solution before use and then air-dried.

In the embodiment of the invention, after electroslag remelting is finished, the feeding operation of reducing power by stages is carried out.

In the embodiment of the invention, the ingot obtained after electroslag remelting is subjected to component detection by adopting an ICP (inductively coupled plasma) and a nitrogen-oxygen analyzer.

The melting temperature of the slag system for smelting the Ce-containing Fe-Ni soft magnetic alloy in the embodiment of the invention is 1200-1300 ℃.

The slag system for smelting Fe-Ni soft magnetic alloy containing Ce in the embodiment of the invention has the resistivity of 0.382-0.578 omega-cm at 1550 +/-5 ℃.

The viscosity of the slag system for smelting the Fe-Ni soft magnetic alloy containing Ce in the embodiment of the invention is 0.015-0.027 Pa.s at 1550 +/-5 ℃.

The preparation method of the slag system for smelting the Ce-containing Fe-Ni soft magnetic alloy in the embodiment of the invention is to mix CaO and Al₂O₃、NaF、MoO₂、MgO、CeO₂、SiO₂And CaF₂And (4) uniformly mixing.

The crushing in the embodiment of the invention is to crush the mixture into small blocks with the diameter of less than 10 mm.

The fluorite powder in the embodiment of the invention is a commercial industrial-grade product.

The alloy scrap in the embodiment of the invention is obtained by crushing the consumable electrode and the alloy material into powder.

In the embodiment of the invention, after the alloy scraps and the fluorite powder are paved, the fluorite powder is filled in the gaps of the alloy scraps.

The mass of the slag system for smelting the Fe-Ni soft magnetic alloy containing Ce in the embodiment of the invention is 10% of the mass of the consumable electrode.

The following are preferred embodiments of the present invention.

Example 1

The slag system for smelting Ce-containing Fe-Ni soft magnetic alloy contains CaO 22% and Al in percentage by mass₂O₃20％，NaF 6％，MoO₂ 2％，MgO 4％，CeO₂ 5％，SiO₂ 1％，CaF₂ 40％；

The using method comprises the following steps:

pre-melting the slag system for smelting the Ce-containing Fe-Ni soft magnetic alloy at 1450 +/-5 ℃ for 15min, and then air-cooling to room temperature and crushing to prepare pre-melted slag lump material;

heating the pre-melted slag lump material to 600 +/-5 ℃, baking for 3h, and cooling to room temperature along with the furnace to prepare pre-melted slag;

alloy scraps are laid on the dummy bar plate, the alloy scraps are positioned at the projection of the consumable electrode on the dummy bar plate, and the laying thickness of the alloy scraps is 40 mm; meanwhile, fluorite powder is paved in the space between the alloy scraps and the inner wall of the crystallizer, and the paving thickness of the fluorite powder is 7 mm; the alloy scrap has the same components as the consumable electrode;

under the condition of argon atmosphere, a consumable electrode is lowered to perform arc striking, and after the arc striking is finished, pre-melted slag is added into a crystallizer to perform slag melting; the calculation formula of the dosage of the premelting slag added into the crystallizer is (650-1250) multiplied by D³kg, wherein D is the inner diameter of the crystallizer; the consumable electrode is Fe-Ni soft magnetic alloy containing Ce, and comprises 14.6% of Fe, 5.2% of Mo, 0.4% of Si, 0.3% of Mn, 0.041% of Ce and the balance of Ni and inevitable impurities by mass percent; the inevitable impurities comprise less than 0.001% of N, less than 0.03% of Al, less than 0.004% of S and less than 0.002% of O;

the inner diameter of the crystallizer is 0.09m, and the adding amount of the pre-melted slag is 650 XD³＝0.47kg；

Forming a slag pool after slagging is finished, carrying out electroslag remelting, adding aluminum particles into the slag pool in the electroslag remelting process, and adding the aluminum particles once every 4 min; adding aluminum particles in an amount which is 0.1 percent of the mass of the consumable electrode melted within 4min until electroslag remelting is completed;

the consumable electrode contains 5.2% of Mo, 0.0033% of S, 0.0015% of O and 0.041% of Ce by mass percent; the cast ingot after electroslag remelting contains 5.09% of Mo, 0.0013% of S, 0.0011% of O and 0.0375% of Ce by mass percent;

carrying out a comparison test by adopting the same consumable electrode and a pseudo-ginseng slag system, and adding no aluminum particles during electroslag remelting to obtain a cast ingot which contains 4.85% of Mo, 0.0018% of S, 0.0018% of O and 0.0129% of Ce in percentage by mass; the pseudo-ginseng slag system contains CaF according to mass percentage₂ 70％，Al₂O₃ 30％；

The comparison shows that when the slag system for smelting the Ce-containing Fe-Ni soft magnetic alloy is used for electroslag remelting, the burning loss of Ce element and Mo element is obviously reduced, and the oxygen content in the cast ingot is lower.

Example 2

The slag system for smelting Ce-containing Fe-Ni soft magnetic alloy contains 27 percent of CaO and Al in percentage by mass₂O₃10％，NaF 4％，MgO 3％，CeO₂ 3％，SiO₂ 2％，CaF₂ 51％；

The method is the same as example 1, except that:

(1) baking the pre-melted slag lump material for 6 hours;

(2) the laying thickness of the alloy chips is 30mm, and the laying thickness of the fluorite powder is 5 mm;

(3) the inner diameter of the crystallizer is 0.15m, and the adding amount of the pre-melted slag is 1250 XD³＝4.22kg；

(4) Adding aluminum particles once every 3 min; the adding amount of the aluminum particles is 0.2 percent of the mass of the consumable electrode melted within 3 min;

(5) the consumable electrodes are divided into three types; the first component comprises 13 percent of Fe, 6.2 percent of Mo, 0.3 percent of Si, 1 percent of Mn, 0.0205 percent of Ce, and the balance of Ni and inevitable impurities, wherein S is 0.0033 percent and O is 0.0014 percent; the second component comprises 50 percent of Fe, 1.8 percent of Mo, 0.15 percent of Si, 0.6 percent of Mn, 0.0159 percent of Ce, and the balance of Ni and inevitable impurities, wherein S is 0.0035 percent and O is 0.0015 percent; the third component comprises, by mass, 31% of Fe, 2.2% of Mo, 0.5% of Si, 0.3% of Mn, 0.0103% of Ce, and the balance of Ni and unavoidable impurities, wherein S is 0.0036% and O is 0.0014% of the unavoidable impurities;

(6) respectively obtaining three kinds of cast ingots after electroslag remelting; the first cast ingot comprises 0.0014 percent of S, 0.0010 percent of O and 0.0181 percent of Ce by mass percent; the second cast ingot comprises 0.0012 percent of S, 0.0012 percent of O and 0.0136 percent of Ce in percentage by mass; the third cast ingot comprises 0.0016 percent of S, 0.0009 percent of O and 0.0089 percent of Ce by mass percent;

the yield of the Ce element is kept at a higher level.

Example 3

Slag systems for smelting Ce-containing Fe-Ni soft magnetic alloy are divided into three types; the first slag system comprises 25 percent of CaO and Al in percentage by mass₂O₃ 20％，NaF 4％，MgO 5％，CeO₂ 3％，SiO₂ 1％，CaF₂42%; the second slag system contains CaO in percentage by mass 22％，Al₂O₃ 10％，NaF 5％，MoO₂ 1％，MgO 4％，CeO₂ 10％，SiO₂1％，CaF₂47%; the third slag system comprises 19 percent of CaO and Al by mass percentage₂O₃ 22％，NaF 6％，MoO₂2％，MgO 3％，CeO₂ 15％，SiO₂ 2％，CaF₂ 31％；

The method is the same as example 1, except that:

(1) baking the pre-melted slag lump material for 5 hours;

(2) the laying thickness of the alloy chips is 50mm, and the laying thickness of the fluorite powder is 10 mm;

(3) the inner diameter of the crystallizer is 0.15m, and the adding amount of the pre-melted slag is 1000 XD³＝3.38kg；

(4) Adding aluminum particles once every 5 min; the adding amount of the aluminum particles is 0.2 percent of the mass of the consumable electrode melted within 5 min;

(5) the consumable electrode comprises, by mass, 41% of Fe, 5.132% of Mo, 0.6% of Si, 0.9% of Mn, 0.0217% of Ce0.0217% of Ni and inevitable impurities in balance; the inevitable impurities comprise less than 0.001 percent of N, less than 0.03 percent of Al, 0.003 percent of S and 0.0015 percent of O;

(6) respectively obtaining three kinds of cast ingots after electroslag remelting; the first cast ingot comprises, by mass, Mo 4.873%, S0.0017%, O0.0012% and Ce 0.0135%; the second cast ingot comprises, by mass, Mo 5.021%, S0.0012%, O0.0011% and Ce 0.0184%; the third cast ingot comprises, by mass, Mo 5.093%, S0.001%, O0.0012% and Ce 0.0196%;

as can be seen, CeO is added into the slag system₂Effective for reducing the burning loss of Ce element, CeO is added₂The yield of Ce and Mo in the alloy after smelting the slag system is greatly improved; for Fe-Ni alloys with different Ce additions, the slag system and the smelting method can effectively reduce the burning loss of easily-oxidized elements in the alloys, and MgO and MoO in the slag system₂、CeO₂The addition of the element(s) can ensure higher yield of Ce and Mo elements.