CN114107686A - Electroslag remelting slag system of high-alloy heat-resistant steel and smelting method - Google Patents
Electroslag remelting slag system of high-alloy heat-resistant steel and smelting method Download PDFInfo
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Abstract
The invention relates to an electroslag remelting slag system of high-alloy heat-resistant steel and a smelting method. The electroslag remelting slag system comprises the following components, namely CaF2：40～80％；Al2O3：10％～30％；CaO：10％～30％；SiO2：0～20％；MgO：0～15％；B2O3: 0 to 5 percent. The smelting method adopting the electroslag remelting slag system specifically comprises the following steps: s1, preparing an electroslag remelting slag system according to the proportion, crushing, stirring uniformly, drying, and taking 10min before smelting; s2, electroslag remelting adopts smelting atmosphere protection, wherein the smelting atmosphere is Ar and N2The oxygen concentration of the mixed gas in the melting atmosphere of (2) is 150ppm or less. The invention provides an electroslag remelting slag system of high-alloy heat-resistant steel, and the slag system formula and the electroslag smelting process can control components Al, Si, B, N and O which are difficult to control in a steel ingot within a specified range, and the components in the steel ingot are more uniform.
Description
Technical Field
The invention belongs to the field of metal smelting, and particularly relates to an electroslag remelting slag system of high-alloy heat-resistant steel and a smelting method.
Background
With the development of the power industry and the increasing global concern on environmental problems, primary energy is saved, environmental protection is enhanced, harmful exhaust emission is reduced, and global greenhouse effect is reduced, which has attracted high attention at home and abroad. The thermal efficiency of the thermal power generating unit is improved, and the adoption of the supercritical unit and the ultra-supercritical unit is one of effective ways for preventing environmental pollution. With the rapid development of supercritical and ultra-supercritical thermal power generating units in China, new materials and new processes are continuously generated, and high-alloy heat-resistant steel such as P91, P92, FB2, Cr12 and the like is generally adopted.
Electroslag remelting is an important special smelting means, the effect of removing large-particle inclusions is obvious, and the purity of steel is improved; the macrosegregation is small, the component uniformity of steel is improved, and the quality stability and reliability of the rotor steel material are improved; the microcosmic segregation is small, and the strength and the toughness of the material are obviously improved; the uniformity of the element distribution can be improved.
The high-alloy heat-resistant steel has high alloy content and high accuracy control difficulty. Elements which need to be specially controlled in the electroslag remelting process of the high-alloy heat-resistant steel comprise Al, Si, B, N, O and the like. At present, the invention patent CN201510923798.1 relates to a method for controlling the oxygen content and the nonmetallic inclusion of P91 electroslag steel, and the invention patent CN201610009905.4 discloses a method for smelting clean steel electroslag steel, and the method can control the nonmetallic inclusion in an electroslag ingot within a specified range. The invention patent CN201910343716.4 relates to a production process method of steel FB2 electroslag for a large-scale ultra-supercritical rotor.
The above patent only discloses a method for controlling non-metallic inclusions in several types of steel, but the control of the element components in these steel types is not related, and how to control the elements difficult to control in the steel types is a very critical problem, and these elements play a decisive role in the influence of the steel performance.
Disclosure of Invention
The technical task of the invention is to provide an electroslag remelting slag system of high alloy heat-resistant steel and a smelting method aiming at the defects of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: an electroslag remelting slag system of high-alloy heat-resistant steel comprises the following components, by mass fraction, CaF2：40～80％；Al2O3：10％～30％；CaO：10％～30％；SiO2：0～20％；MgO：0～15％；B2O3：0～5％。
The invention also provides a method for smelting high-alloy heat-resistant steel by adopting the electroslag remelting slag system, which specifically comprises the following operations:
s1, preparing an electroslag remelting slag system according to the proportion, crushing, stirring uniformly, drying, and taking 10min before smelting;
s2, electroslag remelting adopts smelting atmosphere protection, wherein the smelting atmosphere is Ar and N2The oxygen concentration of the mixed gas in the melting atmosphere of (2) is 150ppm or less.
Further, before electrode smelting, the electrode surface is polished to keep the surface smooth, dry, rust-free and oil-free.
Further, the slag materials of the components before being crushed in the S1 need to be respectively baked according to a baking system.
Further, B in S12O3It is dried separately and then mixed with the remaining slag.
Further, the drying condition in S1 is drying for more than 4 hours at 300 ℃.
Further, the oxygen content of the electrode in the method is below 30 ppm.
Further, the smelting atmosphere in the S2 needs to be subjected to deoxidation and dehydration treatment, wherein Ar is N2The flow ratio of (A) is 9:1 to 3: 7.
The invention uses CaF through phase diagram and thermodynamic analysis2-CaO-Al2O3Basic ternary slag system, CaF in slag component2：40～80％，Al2O3The CaO content is 10 to 30 percent, and the Al content in the slag is reduced2O3Activity, can ensure low Al concentration in steel under a certain oxygen content in steel, and adopts the method of adding SiO into slag through thermodynamic calculation2And B2O3Respectively controlling the contents of Si and B in steel and SiO in slag2、Al2O3With [ Al ] in steel]、[Si]There is an equilibrium reaction as follows:
3(SiO2)+4[Al]＝2(Al2O3)+3[Si]
in the formula, K is an equilibrium constant, a is activity, and if the activity of aluminum oxide and the activity of silicon oxide in slag and the activity of Al in steel are determined values, the activity of Si in steel is a fixed value. The Si activity in the steel can be changed by adjusting the alumina activity and the silica activity in the slag and the Al activity in the steel.
SiO in slag2、B2O3And in steel [ B ]]、[Si]There is an equilibrium reaction as follows:
3(SiO2)+4[B]＝2(B2O3)+3[Si]
where K is the equilibrium constant and a is the activity if [ B ] in the steel]When the activity is high, the SiO in the slag can be increased2Activity, or reduction of B in slag2O3Activity and [ Si ] in steel]Activity to reduce [ B ] in steel]Activity of (d); if [ B ] in the steel]When the activity is low, then the SiO in the slag can be reduced2Activity, or increase of B in slag2O3Activity and [ Si ] in steel]Activity to increase [ B ] in steel]Activity of (c).
In smelting N2And in steel [ N ]]There is an equilibrium reaction as follows:
N2＝2[N]
where K is the equilibrium constant and P is the pressure, if [ N ] in the steel]With low activity, then N can be increased2Partial pressure to increase N activity; if in steel [ N ]]High activity, then it is possible to reduce N2Partial pressure to reduce N activity;
during smelting O2With steel in [ O ]]There is an equilibrium reaction as follows:
O2＝2[O]
where K is the equilibrium constant and P is the pressure, if [ O ] in the steel]With low activity, O may be increased2Partial pressure to increase O activity; if [ O ] in the steel]High activity, then by reducing O2Partial pressure to reduce the O activity.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an electroslag remelting slag system of high-alloy heat-resistant steel through phase diagram and thermodynamic analysis.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following description is of preferred embodiments of the present invention, and it should be understood that the preferred embodiments described herein are for purposes of illustration only and are not intended to limit the invention.
The invention provides an electroslag remelting slag system of high-alloy heat-resistant steel, which comprises the following components in percentage by mass2：40～80％；Al2O3：10％～30％；CaO：10％～30％；SiO2：0～20％；MgO：0～15％；B2O3：0～5％。
The smelting steps adopting the slag system specifically comprise:
1. slag treatment
Al2O3Weighed at 1400 ℃ in Al2O3Drying the crucible for 10 hours, and sealing; weighing MgO, crushing, drying in an MgO crucible at 1100 ℃ for 10 hours, and sealing; b is2O3And then the mixture is weighed,drying the corundum crucible for 10 hours at 300 ℃, and sealing; CaF2Weighing, drying in a corundum crucible at 500 ℃ for 10 hours, and sealing; SiO 22Weighing, drying in a quartz crucible at 1000 ℃ for 10 hours, and sealing; in the drying process, when the temperature in the furnace is reduced to 200-300 ℃ to room temperature, the packaging is carried out quickly, and the moisture in the environment is prevented from being absorbed again;
the method can also be based on the pre-melted slag purchased from the market, weigh and crush the pre-melted slag, dry the pre-melted slag at 300 ℃, and analyze CaF in the pre-melted slag2、Al2O3、CaO、SiO2、MgO、B2O3The content of (A) is sealed, and the slag system needed by the root is added and prepared according to the proportion.
2. Preparation of slag charge
(1) Preparing a slag system required by the invention, fully crushing and mixing, drying at 300 ℃ for more than 4 hours, and taking out 10 minutes before smelting; due to B2O3The melting point of the slag is low, and the slag is added into a slag system after being independently dried;
(2) strictly controlling the weight error of each part of slag charge during slag system proportioning, and reserving 80g of slag charge as a sample;
(3) paving more slag materials on the bottom water tank as much as possible, and adding a small amount of residual slag materials into a hopper;
3. preparatory work before smelting
(1) The electrode diameter is consistent with the diameter of the false electrode, and is
(0+0.5 mm); turning 5-45-degree chamfers at two ends of the electrode; polishing and flattening the welding seams of the electrodes and the false electrodes, wherein the straightness is required to be 0-0.5 mm;
(2) before electrode smelting, polishing the surface, wiping with alcohol, and drying to prevent rust and rust on the surface of the electrode, and ensure that the surface is smooth and dry;
(3) before production, the electrode is placed in a heating furnace for baking at 200 ℃ for 3 hours, lifted out of the heating furnace within 10 minutes before an experiment, and loaded into an electroslag furnace;
(4) polishing and fully drying the surface of the arc striking agent;
(5) polishing and drying the surface of a bottom pad with the same components as the electrode, and drying the bottom pad under the same condition as the consumable electrode;
(6) the tightness of the gas shield cover is checked regularly, the asbestos rope needs to be replaced every furnace time, and the asbestos rope and the electrode are dried together;
(7) the requirements of the protective cover, the inner wall of the crystallizer and the surface of the low water tank are advanced by 3-5 hours, and warm water with the temperature of 40-50 ℃ is introduced to prevent condensation.
4. Air evacuation in crystallizer
(1) High-purity argon is adopted in the experiment, and three bottles are prepared in advance; or adopting common argon gas, connecting a dehumidifying device, and comparing the oxygen content;
(2) detecting the purity of each bottle of protective gas by adopting a method of directly connecting a pipeline to an oxygen content meter, wherein the oxygen content of high-purity argon is 25-35PPM, and the replacement is not satisfied;
(3) emptying in a downward pipe extending mode, sealing the opening of a gas shield cover, and indicating that air is emptied when an oxygen content meter is observed to reach the lowest point (30-50 PPM), inserting an electrode into a crystallizer to prepare for arc starting and slagging;
(4) experiments require that the oxygen content of the atmosphere is kept stable, 50ppm, 70 ppm and 90ppm (within 150) are required, fluctuation is +/-10 ppm, the experiment process tries to find abnormality, search reasons and remedy in time, and if the fluctuation exceeds 30ppm, the abnormality is reported immediately.
(5) According to the requirements, after the experiment is prepared, before the power is switched on, the oxygen concentration of the furnace gas is tested in a cold mode under the condition that a false electrode is not welded, and the tightness is tested in a sealing mode.
5. Operating requirements of the melting stage
(1) Starting arc and adding slag, opening a slag adding port, adding slag as soon as possible, preferably completely adding slag within 2 minutes, closing a slag clamping pipeline after adding slag, and sealing the slag adding port; the hopper is used for feeding materials in a closed mode at one time, and the rest of slag materials are fed into the crystallizer at one time before being electrified and argon is introduced;
(2) when the gas is replaced, the oxygen content is slightly increased when the gas is closed or the gas pressure is insufficient, the gas needs to be replaced quickly, and the replacement is completed within 30 seconds;
(3) monitoring the fluctuation of the oxygen content instrument in the whole process, and checking whether protective gas leakage occurs or not if the fluctuation is abnormal;
(4) after the smelting is finished, maintaining the gas protection for 5 minutes, and then closing the protection gas; and (4) reserving a slag cap and a slag crust sample.
Example 1
The special slag system of Cr12 is: in terms of mass fraction, CaF245% of Al2O310% of CaO, 30% of CaO, SiO25% of MgO content and 10% of MgO content;
the electroslag remelting condition of the Cr12 steel adopting the slag system is as follows: preparing an electroslag remelting slag system according to the proportion, baking, crushing, stirring uniformly, drying, and taking 10min before smelting; drying boron oxide independently and adding into a slag system independently; the oxygen content of the electrode is below 30 ppm; polishing the electrode, keeping the surface smooth, dry, rust-free and oil-free; electroslag remelting adopts mixed gas protection of high-purity argon (purity 98%) and nitrogen (purity 98%), and the mixing ratio is Ar: N21:1 (flow ratio, m)3H) and is subjected to deoxidation and dehydration treatment, and the oxygen concentration of the smelting atmosphere is below 150 ppm.
Three 100kg electroslag ingots are produced by adopting a Cr12 special slag system respectively: the heat standard reaching rate is 100%, T.O is less than or equal to 30ppm, Al is less than or equal to 0.010%, Si is less than or equal to 0.10%, the internal control qualification rate of N content is 100%, and smelting data are shown in a table.
TABLE Cr12 chemical composition/wt%
Example 2
The P91 special slag is as follows: in terms of mass fraction, CaF240% of Al2O330% of CaO, 15% of CaO, SiO210% of MgO content and 5% of MgO content;
adopting the electroslag remelting conditions of the P91 steel of the slag system as follows: preparing an electroslag remelting slag system according to the proportion, baking, crushing, stirring uniformly, drying, and taking 10min before smelting; drying boron oxide independently and adding into a slag system independently; the oxygen content of the electrode is less than 30ppm(ii) a Polishing the electrode, keeping the surface smooth, dry, rust-free and oil-free; electroslag remelting adopts mixed gas protection of high-purity argon (98%) and nitrogen (98%), and the mixing ratio is Ar: N2-9: 1 (flow ratio, m)3H) and is subjected to deoxidation and dehydration treatment, and the oxygen concentration of the smelting atmosphere is below 150 ppm.
Three 100kg electroslag ingots are produced by adopting a P91 special slag system respectively: the heat standard reaching rate is 100%, T.O is less than or equal to 25ppm, Al is less than or equal to 0.040%, Si is less than or equal to 0.2% and less than or equal to 0.5%, the internal control qualification rate of N content is 100%, and smelting data are shown in a table.
TABLE P91 chemical composition/wt%
| Element(s) | C | Si | Mn | P | S |
| Standard of merit | 0.08-0.12 | 0.20-0.50 | 0.30-0.60 | ≤0.020 | ≤0.01 |
| Electroslag ingot | 0.1 | 0.4 | 0.4 | 0.01 | 0.01 |
| Element(s) | V | Nb | Mo | N | Al |
| Standard of merit | 0.18-0.25 | 0.06-0.1 | 0.85-1.05 | 0.03-0.07 | ≤0.04 |
| Electroslag ingot | 0.2 | 0.09 | 1 | 0.05 | 0.03 |
| Element(s) | Cr | Ni | |||
| Standard of merit | 8.0-9.5 | ≤0.4 | |||
| Electroslag ingot | 9 | 0.4 |
Example 3
The special slag system for FB2 is as follows: in terms of mass fraction, CaF250% of Al2O310% of CaO, 10% of SiO220% of MgO content, 5% of MgO content, B2O3The content is 5 percent;
adopting the electroslag remelting conditions of the FB2 steel of the slag system as follows: preparing an electroslag remelting slag system according to the proportion, baking, crushing, stirring uniformly, drying, and taking 10min before smelting; drying boron oxide independently and adding into a slag system independently; the oxygen content of the electrode is below 30 ppm; polishing the electrode, keeping the surface smooth, dry, rust-free and oil-free; electroslag remelting adopts mixed gas of high-purity argon (98%) and nitrogen (98%) for protection, and the mixing ratio is Ar: N21:1 (flow ratio, m)3H) and is subjected to deoxidation and dehydration treatment, and the oxygen concentration of the smelting atmosphere is below 150 ppm.
Three 100kg electroslag ingots are produced by adopting a FB2 special slag system: the heat standard reaching rate is 100%, T.O is less than or equal to 30ppm, Al is less than or equal to 0.010%, Si is less than or equal to 0.10%, the internal control qualification rate of N content is 100%, and smelting data are shown in a table.
TABLE FB2 chemical composition/wt%
| Element(s) | C | Si | Mn | P | S |
| Standard of merit | 0.12-0.15 | ≤0.10 | 0.30-0.50 | ≤0.010 | ≤0.005 |
| Electroslag ingot | 0.13 | 0.1 | 0.4 | 0.01 | 0.005 |
| Element(s) | V | Nb | B | N | Al |
| Standard of merit | 0.15-0.25 | 0.04-0.06 | 0.008-0.011 | 0.015-0.030 | ≤0.010 |
| Electroslag ingot | 0.2 | 0.05 | 0.01 | 0.02 | 0.01 |
| Element(s) | Cr | Ni | Mo | Co | |
| Standard of merit | 9.00-9.40 | 0.10-0.20 | 1.40-1.60 | 0.90-1.30 | |
| Electroslag ingot | 9.2 | 0.15 | 1.5 | 1 | |
| Element(s) | Cu | As | Sn | Sb | |
| Standard of merit | ≤0.15 | ≤0.020 | ≤0.015 | ≤0.0015 | |
| Electroslag ingot | 0.15 | 0.02 | 0.015 | 0.0015 |
Example 4
The P92 special slag is: in terms of mass fraction, CaF280% of Al2O310% of CaO and 10% of CaO;
adopting the electroslag remelting conditions of the P92 steel of the slag system as follows: preparing an electroslag remelting slag system according to the proportion, baking, crushing, stirring uniformly, drying, and taking 10min before smelting; drying boron oxide independently and adding into a slag system independently; the oxygen content of the electrode is below 30 ppm; polishing the electrode, keeping the surface smooth, dry, rust-free and oil-free; electroslag remelting adopts mixed gas of high-purity argon (98%) and nitrogen (98%) for protection, and the mixing ratio is Ar: N23:7 (flow ratio, m)3H) and is subjected to deoxidation and dehydration treatment, and the oxygen concentration of the smelting atmosphere is below 150 ppm.
Three 100kg electroslag ingots are produced by adopting a P92 special slag system respectively: the heat standard reaching rate is 100%, T.O is less than or equal to 25ppm, Al is less than or equal to 0.010%, Si is less than or equal to 0.10%, the internal control qualification rate of N content is 100%, and smelting data are shown in a table.
TABLE P92 chemical composition/wt%
The technical idea of the present invention is described in the above technical solutions, and the protection scope of the present invention is not limited thereto, and any changes and modifications made to the above technical solutions according to the technical essence of the present invention belong to the protection scope of the technical solutions of the present invention.
Claims (8)
1. The electroslag remelting slag system of the high-alloy heat-resistant steel is characterized by comprising the following components, namely CaF2：40～80％；Al2O3：10％～30％；CaO：10％～30％；SiO2：0～20％；MgO：0～15％；B2O3：0～5％。
2. A method for smelting high-alloy heat-resistant steel based on the electroslag remelting slag system of claim 1 is characterized by comprising the following steps:
s1, preparing an electroslag remelting slag system according to a ratio, crushing, stirring uniformly, drying, and taking 10min before smelting;
s2, electroslag remelting adopts smelting atmosphere protection, wherein the smelting atmosphere is Ar and N2The oxygen concentration of the mixed gas in the melting atmosphere of (2) is 150ppm or less.
3. The method for smelting high alloy heat resistant steel according to claim 2, wherein before the electrode is smelted, the surface of the electrode is polished to keep the surface smooth, dry, rust-free and oil-free.
4. The method of smelting a high alloy, heat resistant steel according to claim 2, wherein the electrode oxygen content in the method is 30ppm or less.
5. The method for smelting a high alloy heat resistant steel according to claim 2, wherein the slag materials of the components before crushing in S1 are baked according to a baking schedule.
6. The method for producing high alloy heat resistant steel as claimed in claim 2, wherein B in S12O3It is dried separately and then mixed with the remaining slag.
7. The method for smelting a high alloy heat resistant steel according to claim 2, wherein the drying condition in S1 is drying at 300 ℃ for 4 hours or more.
8. The method for smelting high-alloy heat-resistant steel according to claim 2, wherein the smelting atmosphere in S2 is subjected to deoxidation and dehydration treatment, wherein Ar is N2The flow ratio of (A) is 9:1 to 3: 7.
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| CN114854993A (en) * | 2022-03-30 | 2022-08-05 | 重庆材料研究院有限公司 | Seawater corrosion resistant high-strength stainless steel electroslag remelting slag system |
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