CN111876609B - Oxide-reinforced low-activation steel, electroslag remelting slag system and smelting method - Google Patents
Oxide-reinforced low-activation steel, electroslag remelting slag system and smelting method Download PDFInfo
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Abstract
The invention discloses oxide-reinforced low-activation steel, an electroslag remelting slag system and a smelting method, wherein the electroslag remelting slag system comprises slag A and slag B, and the slag A comprises the following components in parts by mass: CaF240 to 55 parts of Y2O330 to 35 parts of CaO, 20 to 30 parts of CaO; the component of the B slag comprises CaF255 to 65 parts, CaO 30 to 40 parts, MgO 2 to 5 parts, SiO23 to 7 parts; during smelting, a blind hole is processed inwards from the upper end face of the consumable electrode, yttrium is filled in the blind hole, the upper end of the consumable electrode is welded with the dummy electrode, the consumable electrode is fixed at a smelting position, slag A is added into a water-cooled crystallizer, and arc starting and slag forming are carried out; starting smelting after arc starting, adding B slag after the smelting reaches the specified position of the consumable electrode, and continuing smelting until the smelting is finished, wherein the specified position is a horizontal position corresponding to the bottom of the blind hole in the consumable electrode. The electroslag remelting slag system does not contain Al2O3The smelting method can fully utilize the electroslag remelting system of the invention, improve the Y yield and obtain new oxide reinforced low-activation steel.
Description
Technical Field
The invention relates to the field of electric metallurgy, in particular to an oxide reinforced low-activation steel, an electroslag remelting slag system and a smelting method.
Background
Low activation steel is generally considered as the first choice structural material for future fusion demonstration reactors and fusion power reactors due to its excellent performance. It adopts a design of low activation, namely the radioactivity of the material after service is required to be reduced to a limit level (10mSv/h) which can be recycled within 100 years, so that the existence of high-activity elements Al, Ni, Cu, Nb, Mo and Sn in the steel is avoided. In order to improve the mechanical property of the low-activation steel in one step, scholars at home and abroad develop Y by applying a powder metallurgy process through a large amount of experimental researches2O3Oxide-strengthened low activation steel. At present, the problems of uniform dispersion of oxide dispersed phases in parent metal and low-temperature brittleness of materials in the process of preparing oxide reinforced steel by adopting a powder metallurgy method are not well solvedMeanwhile, the reproducibility of the process and the product is poor, and the steel with the same purity and the same structure and performance is difficult to prepare. The smelting process can effectively solve the problems.
At present, the vacuum induction melting technology and the electroslag remelting technology are widely adopted internationally to prepare low-activation steel. Vacuum Induction Melting (VIM) refers to a method for heating furnace burden by using eddy current generated in a metal conductor by electromagnetic Induction under a Vacuum condition, is convenient for controlling temperature and pressure, and has the advantages of small volume of a Melting chamber, short vacuumizing time and Melting period and the like. Electroslag remelting is a method of melting using resistance heat generated when current passes through slag as a heat source. The main purpose is to purify the metal and obtain a clean, uniform and compact steel ingot. The steel remelted by electroslag has high purity, low sulfur content, less non-metallic inclusions, smooth steel ingot surface, cleanness, uniformity and compactness, and uniform metallographic structure and chemical components. Meanwhile, the electroslag remelting process has the advantages of simple equipment, convenient operation and higher stability and controllability of the process.
The current slag system commonly used for electroslag remelting is CaF2Adding A1 as main raw material2O3Oxides such as CaO and the like; the basic slag system is CaF2-A12O3Slag system (70% CaF)2-30%A12O3) And CaF2-CaO-A12O3Slag system (60% CaF)2-20%A12O320% CaO and 40% CaF2-30%A12O330 percent of CaO) and the slag systems contain A1 with certain mass fraction2O3A1 in smelting process2O3The entering molten steel causes pollution to the low activation steel, and the activity of the low activation steel is increased. At the same time Y2O3The rare earth oxide has the advantage that the problem that the recovery rate of the rare earth is extremely low (less than 5%) in the electroslag remelting process is not solved all the time. Therefore, there is a high necessity for a novel Al-free alloy2O3The electroslag slag system capable of improving the Y yield is used for smelting the oxide reinforced low-activation steel.
Disclosure of Invention
To solve the problems of the prior art, the present invention aims atThe electroslag remelting slag system does not contain Al2O3The smelting method can fully utilize the electroslag remelting system, improve the Y yield and obtain new oxide reinforced low-activation steel.
The technical scheme adopted by the invention is as follows:
the electroslag remelting slag system for the oxide-reinforced low-activation steel comprises slag A and slag B, wherein the slag A comprises the following components in parts by mass: CaF240 to 55 parts of Y2O330 to 35 parts of CaO, 20 to 30 parts of CaO; the component of the B slag comprises CaF255 to 65 parts, CaO 30 to 40 parts, MgO 2 to 5 parts, SiO 23 to 7 parts;
the electroslag remelting slag system is suitable for smelting oxide reinforced low-activation steel with the following components in percentage by mass: c: 0.09% -0.12%, Si: 0.15% -0.23%, Mn: 0.13-0.18%, Cr: 7.5% -8.4%, W: 1.7% -2.0%, V: 0.18-0.19%, Ti: 0.018-0.048%, Zr: 0.016 to 0.04 percent, and Y2O3: 0.24-0.27 percent of the total weight of the alloy, and the balance of Fe.
A smelting method of oxide reinforced low-activation steel comprises the following steps:
s1, machining a blind hole inwards from the end face of the upper end of the consumable electrode, filling yttrium in the blind hole, welding the upper end of the consumable electrode with a dummy electrode, fixing the consumable electrode at a smelting position, adding the slag A into a water-cooled crystallizer, and carrying out arc starting and slagging;
s2, starting smelting after arcing, adding the slag B after smelting to the specified position of the consumable electrode, and continuing smelting until finishing, wherein the specified position is the horizontal position corresponding to the bottom of the blind hole on the consumable electrode;
the consumable electrode is made of vacuum induction smelting low-activation steel;
the mass ratio of the yttrium to the consumable electrode is (0.5-1.5)/100; the dosage of the A slag is 8 to 10 percent of the mass of the part from the lower end of the consumable electrode to the bottom of the blind hole, and the dosage of the B slag is 10 to 15 percent of the total weight of the consumable electrode;
the oxide reinforced low-activation steel obtained by smelting comprises the following components in percentage by mass: c: 0.09% -0.12%, Si: 0.15% -0.23%, Mn: 0.13-0.18%, Cr: 7.5% -8.4%, W: 1.7% -2.0%, V: 0.18-0.19%, Ti: 0.018-0.048%, Zr: 0.016 to 0.04 percent, and Y2O3: 0.24-0.27 percent of the total weight of the alloy, and the balance of Fe.
Preferably, the chemical composition of the vacuum induction smelting low-activation steel comprises the following components in percentage by mass: c: 0.10% -0.13%, Si: 0.15-0.25%, Mn: 0.15-0.25%, Cr: 7.7% -8.7%, W: 1.7% -2.3%, V: 0.20-0.25%, Ti: 0.02% -0.06%, Zr: 0.02-0.06 percent, and the balance of Fe.
Preferably, the slag A and the slag B are both subjected to baking pretreatment before use, the baking pretreatment temperature is 600-700 ℃, and the baking pretreatment time is at least 6 hours.
Preferably, the distance from the lower end of the consumable electrode to the bottom of the blind hole is 1/15-1/10 of the total length of the consumable electrode.
Preferably, the blind holes are filled with yttrium powder, and the particle size of the yttrium powder is less than or equal to 35 microns.
The invention also provides the oxide reinforced low-activation steel obtained by smelting through the smelting method.
Preferably, the oxide-reinforced low-activation steel comprises the following components in percentage by mass: c: 0.09% -0.12%, Si: 0.15% -0.23%, Mn: 0.13-0.18%, Cr: 7.5% -8.4%, W: 1.7% -2.0%, V: 0.18-0.19%, Ti: 0.018-0.048%, Zr: 0.016 to 0.04 percent, and Y2O3: 0.24-0.27 percent of the total weight of the alloy, and the balance of Fe.
The invention has the following beneficial effects:
the electroslag remelting slag system for the oxide-reinforced low-activation steel mainly takes the principle that the low-activation steel cannot contain Al element and the strength of the low-activation steel is improved as the starting point, and combines the oxide-reinforced low-activation steelThe oxide particles in (A) are Y2O3And redesigning the electroslag remelting slag system. Because the traditional electroslag remelting slag system contains Al2O3The components are smelted by adopting the slag system, Al in the slag enters molten steel, the molten steel is polluted, and the activity of steel is further improved. The radioactivity of the steel cannot be guaranteed to be reduced to the limit level (10mSv/h) which can be recycled within 100 years after service, the slag system designed by the invention does not contain high-activity element Al, the problem can be effectively avoided, and Y is added into the steel2O3Can improve the yield of Y, and is added with partial SiO2And MgO can lower the slag system melting point and improve its fluidity. Ti, Zr and Y are simultaneously introduced into the oxide reinforced steel2O3The addition of Ti and Zr can effectively improve the quantity of MX phases in the steel, increase the strengthening effect of the second phase, and the melting point of the MX phases containing Ti and Zr is higher, so that the high-temperature mechanical property of the steel can be improved. With Ti, Zr and Y2O3Can combine and generate Y-Ti-O, Y-Zr-O and Y-Ti-Zr-O phases with smaller size and more stable performance, play a good role in dispersion strengthening and further improve the mechanical property of steel.
Compared with the traditional smelting process, the smelting method of the oxide reinforced low-activation steel adopts a two-stage slag adding mode in the smelting process, the slag A is adopted in the first stage, normal arcing and slagging in the electroslag process are guaranteed, the requirement of the initial smelting stage is met, the slag B is combined with metal yttrium refining of a consumable electrode core part in the second stage, and the reinforcing phase Y can be introduced into the steel on the premise of reducing the oxygen mass fraction in the steel2O3. According to the smelting method, the metal yttrium is sealed in the electrode and isolated from the air, so that the oxidation of the metal yttrium before the metal yttrium is contacted with the liquid electroslag slag system can be avoided, and the product of the deoxidized metal yttrium is Y2O3The oxide-reinforced steel can not pollute molten steel, and can also be used as a reinforced phase to enter the molten steel to form the oxide-reinforced steel.
Further, the temperature of the baking pretreatment is 600-700 ℃, the time is at least 6 hours, free water and bound water in slag can be completely removed, the hydrogen content in molten steel is ensured, and meanwhile, the baking pretreatment is carried out at the temperatureCan also avoid CaF2Causing the change of the slag system components.
Furthermore, the distance from the lower end of the consumable electrode to the bottom of the blind hole is 1/15-1/10 of the total length of the consumable electrode, the main task of the electroslag remelting initial stage is arcing and slagging, and after the smelting is finished, the front section of the cast ingot needs to be cut off, so that the part of the front section which does not contain yttrium is not easy to overlong, and the waste is prevented. The property of yttrium is very active and is not beneficial to arcing, so that the front section of the consumable electrode does not contain yttrium, and the part without yttrium is not too short easily, thereby preventing arcing and slagging failure.
Furthermore, yttrium powder is filled in the blind holes, the particle size of the yttrium powder is less than or equal to 35 microns, the reaction rate can be increased, the yttrium powder is easy to disperse uniformly, the components of the steel are more uniform, and the reaction product Y is beneficial to being prepared2O3The dispersion is uniformly dispersed in the steel, and the dispersion strengthening effect is achieved.
The oxide-reinforced low-activation steel is prepared in a smelting mode, an oxide reinforcing phase is uniformly dispersed in the steel, the material has good low-temperature impact property, the reproducibility of the process and the reproducibility of products are good, the purity of the material is high, the mechanical property is excellent, and the steel does not contain high-activity element aluminum.
Drawings
FIG. 1 is a schematic view of a consumable electrode of the present invention.
In the figure, 1-consumable electrode, 2-blind hole, 3-yttrium.
Detailed Description
The invention is further described below with reference to the figures and examples.
The electroslag remelting slag system for the oxide-reinforced low-activation steel comprises slag A and slag B, wherein the slag A comprises the following components in parts by mass: CaF240 to 55 parts of Y2O330 to 35 parts of CaO, 20 to 30 parts of CaO; the component of the B slag comprises CaF255 to 65 parts, CaO 30 to 40 parts, MgO 2 to 5 parts, SiO 23 to 7 parts;
the electroslag remelting slag system is suitable for smelting oxide reinforced low-activation steel with the following components in percentage by massThe steel comprises the following components: c: 0.09% -0.12%, Si: 0.15% -0.23%, Mn: 0.13-0.18%, Cr: 7.5% -8.4%, W: 1.7% -2.0%, V: 0.18-0.19%, Ti: 0.018-0.048%, Zr: 0.016 to 0.04 percent, and Y2O3: 0.24-0.27 percent of the total weight of the alloy, and the balance of Fe.
The smelting method of the oxide reinforced low-activation steel comprises the following steps:
the consumable electrode is made of vacuum induction smelting low-activation steel, and the vacuum induction smelting low-activation steel comprises the following chemical components in percentage by mass: c: 0.10% -0.13%, Si: 0.15% -0.25%, Mn: 0.15-0.25%, Cr: 7.7% -8.7%, W: 1.7% -2.3%, V: 0.20-0.25%, Ti: 0.02% -0.06%, Zr: 0.02-0.06 percent and the balance of Fe;
the mass ratio of the yttrium to the consumable electrode is (0.5-1.5)/100; the dosage of the A slag is 8 to 10 percent of the mass of the part from the lower end of the consumable electrode to the bottom of the blind hole, and the dosage of the B slag is 10 to 15 percent of the total weight of the consumable electrode;
the oxide reinforced low-activation steel obtained by smelting by the smelting method comprises the following components in percentage by mass: c: 0.09 to 0.12 percent,Si:0.15%~0.23%,Mn:0.13%~0.18%,Cr:7.5%~8.4%,W:1.7%~2.0%,V:0.18%~0.19%,Ti:0.018%~0.048%,Zr:0.016%~0.04%,Y2O3: 0.24-0.27 percent of the total weight of the alloy, and the balance of Fe.
Example 1
In the electroslag remelting slag system of the embodiment, the slag a comprises the following components in parts by mass: CaF240 parts of Y2O333 portions of CaO, 30 portions of CaO; the component of the B slag comprises CaF265 portions of CaO, 30 portions of CaO, 4 portions of MgO and SiO27 parts of;
the smelting method of the oxide reinforced low-activation steel comprises the following steps:
the consumable electrode is made of vacuum induction smelting low-activation steel, and the vacuum induction smelting low-activation steel comprises the following chemical components in percentage by mass: c: 0.10%, Si: 0.25%, Mn: 0.2%, Cr: 8.7%, W: 2.0%, V: 0.20%, Ti: 0.04%, Zr: 0.06 percent and the balance of Fe;
the mass ratio of yttrium to consumable electrode is 0.5/100; the using amount of the slag A is 10% of the mass of the part from the lower end of the consumable electrode to the bottom of the blind hole, and the using amount of the slag B is 12% of the total weight of the consumable electrode;
the oxide reinforced low-activation steel obtained by smelting by the smelting method comprises the following components in percentage by mass: 0.09%, Si: 0.23%, Mn: 0.18%, Cr: 8.3%, W: 2.0%, V: 0.19%, Ti: 0.037%, Zr: 0.04%, Y2O3: 0.27% and the balance Fe. The yield of Y in this example was 43%.
Indexes of the oxide-strengthened low-activation steel obtained by smelting in the embodiment are shown in table 1.
Example 2
In the electroslag remelting slag system of the embodiment, the slag a comprises the following components in parts by mass: CaF250 parts of Y2O330 portions of CaO and 20 portions of CaO; the component of the B slag comprises CaF260 portions of CaO, 35 portions of CaO, 2 portions of MgO and SiO25 parts of;
the smelting method of the oxide reinforced low-activation steel comprises the following steps:
the consumable electrode is made of vacuum induction smelting low-activation steel, and the vacuum induction smelting low-activation steel comprises the following chemical components in percentage by mass: c: 0.12%, Si: 0.15%, Mn: 0.15%, Cr: 7.7%, W: 2.3%, V: 0.25%, Ti: 0.02%, Zr: 0.02% and the balance Fe;
the mass ratio of yttrium to consumable electrode is 1.5/100; the using amount of the slag A is 9% of the weight of the part from the lower end of the consumable electrode to the bottom of the blind hole, and the using amount of the slag B is 15% of the total weight of the consumable electrode;
the oxide reinforced low-activation steel obtained by smelting by the smelting method comprises the following components in percentage by mass: c: 0.11%, Si: 0.15%, Mn: 0.13%, Cr: 7.5%, W: 1.8%, V: 0.19%, Ti: 0.018%, Zr: 0.016%, Y2O3: 0.24% and the balance Fe. The yield of Y in this example was 13%.
Indexes of the oxide-strengthened low-activation steel obtained by smelting in the embodiment are shown in table 1.
Example 3
In the electroslag remelting slag system of the embodiment, the slag a comprises the following components in parts by mass: CaF255 parts by weight of Y2O335 parts of CaO, 25 parts of CaO; the component of the B slag comprises CaF255 parts of CaO, 40 parts of CaO, 5 parts of MgO and SiO 23 parts of;
the smelting method of the oxide reinforced low-activation steel comprises the following steps:
the consumable electrode is made of vacuum induction smelting low-activation steel, and the vacuum induction smelting low-activation steel comprises the following chemical components in percentage by mass: c: 0.13%, Si: 0.20%, Mn: 0.25%, Cr: 8.5%, W: 1.7%, V: 0.22%, Ti: 0.06%, Zr: 0.04 percent and the balance of Fe;
the mass of yttrium to consumable electrode mass ratio is 1/100; the using amount of the slag A is 10% of the weight of the part from the lower end of the consumable electrode to the bottom of the blind hole, and the using amount of the slag B is 10% of the total weight of the consumable electrode;
the oxide reinforced low-activation steel obtained by smelting by the smelting method comprises the following components in percentage by mass: c: 0.12%, Si: 0.18%, Mn: 0.17%, Cr: 8.4%, W: 1.7%, V: 0.18%, Ti: 0.048%, Zr: 0.035%, Y2O3: 0.25 percent and the balance of Fe. The yield of Y in this example was 20%.
Indexes of the oxide-strengthened low-activation steel obtained by smelting in the embodiment are shown in table 1.
TABLE 1
As can be seen from Table 1, the yield strength of the experimental steel at room temperature is 678-689 MPa, the yield strength at 350 ℃ is 516-532 MPa, the yield strength at 550 ℃ is 434-471 MPa, the yield strength at 650 ℃ is 351-361 MPa, the DBTT is-93-101 ℃, and the recovery rate of Y is 13-43%. The implementation of the invention well solves the problems of uniform dispersion of oxide dispersed phase in parent metal and low-temperature brittleness of the material in the process of preparing the oxide reinforced steel by adopting a powder metallurgy method, and simultaneously realizes the Al-free2O3Electroslag smelting improves the recovery rate of the rare earth Y.
Claims (5)
1. The smelting method of the oxide reinforced low-activation steel is characterized by comprising the following steps of:
s1, machining a blind hole inwards from the end face of the upper end of the consumable electrode, filling yttrium in the blind hole, welding the upper end of the consumable electrode with a dummy electrode, fixing the consumable electrode at a smelting position, adding slag A into a water-cooled crystallizer, and carrying out arc starting and slag making;
s2, starting smelting after arcing, adding B slag after the smelting reaches the specified position of the consumable electrode, and continuing to smelt until the smelting is finished, wherein the specified position is a horizontal position corresponding to the bottom of the blind hole in the consumable electrode;
the consumable electrode is made of vacuum induction smelting low-activation steel;
the mass ratio of the yttrium to the consumable electrode is (0.5-1.5)/100; the using amount of the slag A is 8-10% of the mass of the part from the lower end of the consumable electrode to the bottom of the blind hole, and the using amount of the slag B is 10-15% of the total weight of the consumable electrode;
the oxide reinforced low-activation steel obtained by smelting comprises the following components in percentage by mass: c: 0.09% -0.12%, Si: 0.15% -0.23%, Mn: 0.13% -0.18%, Cr: 7.5% -8.4%, W: 1.7% -2.0%, V: 0.18% -0.19%, Ti: 0.018% -0.048%, Zr: 0.016% -0.04% of Y2O3: 0.24% -0.27% of Fe, and the balance of Fe;
the slag A comprises the following components in parts by mass: CaF240 to 55 parts of Y2O330 to 35 parts of CaO, 20 to 30 parts of CaO; the component of the B slag comprises CaF255 to 65 parts, CaO 30 to 40 parts, MgO 2 to 5 parts, SiO23 to 7 parts.
2. The method for smelting the oxide reinforced low-activation steel according to claim 1, wherein the chemical composition of the vacuum induction smelted low-activation steel comprises the following components in percentage by mass: c: 0.10% -0.13%, Si: 0.15% -0.25%, Mn: 0.15% -0.25%, Cr: 7.7% -8.7%, W: 1.7% -2.3%, V: 0.20% -0.25%, Ti: 0.02% -0.06%, Zr: 0.02% -0.06% and the balance of Fe.
3. The method for smelting the oxide reinforced low-activation steel according to claim 1, wherein the slag A and the slag B are both subjected to baking pretreatment before use, the baking pretreatment temperature is 600-700 ℃, and the time is at least 6 hours.
4. The method for smelting an oxide-reinforced low-activation steel as claimed in claim 1, wherein the distance from the lower end of the consumable electrode to the bottom of the blind hole is 1/15-1/10 of the total length of the consumable electrode.
5. The method for smelting oxide-reinforced low-activation steel as claimed in claim 1, wherein the blind holes are filled with yttrium powder, and the particle size of yttrium powder is less than or equal to 35 μm.
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JPS52114503A (en) * | 1976-03-24 | 1977-09-26 | Hitachi Ltd | Slag for remelting electroslag |
CN101328562B (en) * | 2008-07-17 | 2011-01-26 | 中国科学院等离子体物理研究所 | Oxide dispersion strengthening low activity martensitic steel material and preparation thereof |
CN101709384A (en) * | 2009-11-26 | 2010-05-19 | 上海大学 | Novel slag system for improving quality of electroslag remelted steel ingots |
CN102560257B (en) * | 2012-03-02 | 2014-01-22 | 华中科技大学 | Low-activated steel structure material for fusion reactor |
CN102628142B (en) * | 2012-05-03 | 2013-07-03 | 北京科技大学 | Preparation method of low-activation steel for nuclear fusion |
CN105274445B (en) * | 2014-06-06 | 2017-06-13 | 中国科学院金属研究所 | A kind of oxide dispersion intensifying low activation steel and preparation method thereof |
CN106756434B (en) * | 2016-12-05 | 2018-08-03 | 东北大学 | Oxide dispersion intensifying low activation ferrite/martensite steel and its smelting process |
CN109112319B (en) * | 2018-09-18 | 2020-11-10 | 重庆材料研究院有限公司 | Slag for nuclear-grade stainless steel electroslag remelting and method for electroslag remelting by using slag |
CN109609849A (en) * | 2018-12-28 | 2019-04-12 | 西安交通大学 | One kind low activation martensitic steel containing Si and its heat treatment method |
CN111139362B (en) * | 2019-12-14 | 2022-03-08 | 张家港广大特材股份有限公司 | Remelting method of high-purity 316LN stainless steel |
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