WO2021036226A1 - Large-size high-niobium and high-temperature 706 alloy ingot and smelting process thereof - Google Patents

Large-size high-niobium and high-temperature 706 alloy ingot and smelting process thereof Download PDF

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WO2021036226A1
WO2021036226A1 PCT/CN2020/078719 CN2020078719W WO2021036226A1 WO 2021036226 A1 WO2021036226 A1 WO 2021036226A1 CN 2020078719 W CN2020078719 W CN 2020078719W WO 2021036226 A1 WO2021036226 A1 WO 2021036226A1
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electroslag
rate
ingot
temperature
remelting
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PCT/CN2020/078719
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French (fr)
Chinese (zh)
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黄烁
赵光普
张北江
段然
秦鹤勇
李连鹏
丑英玉
齐超
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北京钢研高纳科技股份有限公司
抚顺特殊钢股份有限公司
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Publication of WO2021036226A1 publication Critical patent/WO2021036226A1/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16Remelting metals
    • C22B9/18Electroslag remelting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/023Alloys based on nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • C22C30/02Alloys containing less than 50% by weight of each constituent containing copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

Definitions

  • the invention relates to the technical field of large-size high-niobium alloys, and more specifically, it relates to a large-size high-niobium high-temperature 706 alloy ingot and its smelting process.
  • the 706 superalloy is a special alloy.
  • elements chromium, tungsten, molybdenum, etc.
  • the base metal atoms such as nickel
  • it causes the distortion of the base metal lattice, which can be reduced by adding Alloy matrix stacking fault energy elements (such as cobalt) and adding elements that can slow down the diffusion rate of matrix elements (tungsten, molybdenum, etc.) to strengthen the matrix.
  • Alloy matrix stacking fault energy elements such as cobalt
  • the second phase ⁇ ', ⁇ ", carbide, etc.
  • the structure of the ⁇ 'phase is the same as that of the matrix, which is a face-centered cubic structure, and the lattice constant is The matrix is similar and coherent with the crystal, so the ⁇ 'phase can be uniformly precipitated in the matrix in the form of fine particles, which hinders the movement of dislocations and produces a significant strengthening effect.
  • the ⁇ 'phase is an A3B type intermetallic compound, and A represents nickel, Cobalt, B represents aluminum, titanium, niobium, tantalum, vanadium, and tungsten, while chromium, molybdenum, and iron can be either A or B.
  • the typical ⁇ 'phase in nickel-based alloys is Ni3(Al, Ti), ⁇ "
  • the phase is a body-centered tetragonal structure, and its composition is Ni3Nb. Because the mismatch between the ⁇ " phase and the matrix is large, it can cause a large degree of coherent distortion, so that the alloy can obtain a high yield strength, but when it exceeds 700 °C, it is strengthened. The effect is significantly reduced, and special treatment processes are required. Moreover, for the 706 alloy containing Al and Ti elements, the burning of Al and Ti elements is prone to occur during the electroslag remelting process, which is also an urgent problem to be solved in the preparation process.
  • the triple smelting process of "vacuum induction melting + electroslag remelting + vacuum consumable remelting" is generally used for high-temperature large ingots of more than 10 tons produced in Europe and the United States.
  • the patent US20020170386A1 provides a triple smelting process for large ingots with an alloy diameter of 762 mm or more. During the use of this triple smelting equipment, the diameter of the ingot type and the electrode needs to be matched.
  • the patent provides several examples of the matching of the ingot type and the electrode.
  • the first object of the present invention is to provide a large-size high-niobium high-temperature 706 alloy ingot, the weight of the obtained ingot can reach at least 15 tons, and there is no metallurgical defects such as black spots and white spots. , Ti element has no obvious burning loss.
  • the bar forged from the ingot has been inspected by non-destructive flaw detection, and it is found that there is no abnormal signal at the electroslag remelting joint.
  • the second object of the present invention is to provide a smelting process for the above-mentioned large-size high-niobium high-temperature 706 alloy ingots, which realizes the smelting of large-size high-niobium high-temperature alloy ingots with an ingot weight of 15 tons or more and a diameter of 800 mm or more.
  • the smelting process is Al, Ti element has no obvious burning loss, can effectively prevent the problem of hot cracking, minimize the formation of black and white metallurgical defects, reduce the degree of element segregation, and improve the thermoplasticity of the steel ingot.
  • the present invention provides the following technical solution: a large-size high-niobium high-temperature 706 alloy ingot, characterized in that the high-niobium high-temperature alloy large-size ingot has a diameter of 800mm or more, and is calculated by mass percentage.
  • the chemical composition of the large-size high-niobium high-temperature 706 alloy ingot is:
  • the smelting process of large-size high-niobium high-temperature 706 alloy ingot provided by the present invention includes the following steps:
  • Vacuum induction smelting According to the designed alloy composition requirements, the pure metal raw materials and/or return materials are weighed according to the required elements of the alloy per unit weight as raw materials, and vacuum induction smelting is performed to control the Ni content in the smelting mother liquor to 40.0-43.0wt%. Nb content is 2.80 ⁇ 3.3wt%, Ti content is 0.5 ⁇ 2.0wt%, Al content is 0.2 ⁇ 0.5wt%, and multiple vacuum induction ingots with the same composition are poured;
  • Exchange electroslag remelting the same number of electroslag electrodes are prepared by using the vacuum induction ingots made; all the prepared electroslag electrodes are used, and the exchange electroslag remelting is performed under argon protection.
  • the slag system used is ( CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag, (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag contains 60 ⁇ 75wt% of CaF 2 and 10 ⁇ 25wt% of CaO.
  • Al 2 O 3 accounts for 8 to 13 wt%, and TiO 2 accounts for 1 to 10 wt%; after the exchange electroslag remelting is completed, it is cooled and demolded to obtain an electroslag ingot:
  • Primary vacuum consumable remelting the demolded electroslag ingot is subjected to primary annealing, secondary annealing, forging and drawing to a predetermined size to obtain a primary consumable electrode, wherein the secondary annealing temperature is higher than the primary annealing temperature; then use A consumable electrode is remelted once in vacuum;
  • Secondary vacuum consumable remelting the primary consumable remelted ingots obtained by the primary vacuum consumable remelting, car light, flat head and tail, to obtain a secondary consumable electrode; then use the secondary consumable electrode for secondary vacuum Consumable remelting to prepare ingots of target diameter
  • the Al content in the smelting mother liquor is controlled to be between 0.2 and 0.5 wt%, and the additional Al can be used as a deoxidizer to a certain extent, and remelting process using (CaF 2 -CaO-Al 2 O 3 -TiO 2) and four yuan slag (CaF 2 -CaO-Al 2 O 3 -TiO 2) four yuan CaF 2 slag accounts for 60 ⁇ 75wt %, CaO accounts for 10-25wt%, Al 2 O 3 accounts for 8-13wt%, TiO 2 accounts for 1-10wt%.
  • the composition of each part of the slag system especially the content of TiO 2
  • the content of TiO 2 in the slag system is controlled to 1-10wt%, which can solve the burning problem of Ti element at the head and tail of the electroslag ingot, and also ensure the uniformity of the Ti composition in the electroslag ingot, and minimize the easily oxidized elements
  • a conventional tonnage such as 12 tons
  • vacuum induction furnace is used to prepare multiple induction ingots with the same composition (this also reduces the requirement for the weight of a single induction ingot), In this way, a plurality of electroslag electrodes are prepared, and then electrode exchange remelting is used to prepare large-tonnage electroslag ingots, and then two vacuum consumable remeltings are carried out.
  • one vacuum consumable remelting can improve the electrode exchange joint.
  • Metallurgical quality, and then through secondary vacuum consumable remelting, can completely solve the metallurgical quality problem, so as to prepare high-quality, non-metallurgical defects of at least 15 tons of high-temperature alloy large-size consumable ingot.
  • the total weight of multiple vacuum induction ingots should be 125% to 160% of the target weight of the ingot.
  • the melting temperature is 1300-1550°C.
  • refining is carried out under electromagnetic stirring for 15-120 minutes, and the refining temperature is 1350-1550°C; then cooling for 1-10 hours
  • the mold is demolded to obtain a vacuum induction ingot; the vacuum induction smelting process is repeated many times, and there are many vacuum induction ingots with the same composition.
  • the method of preparing the electroslag electrode is to directly stress-relieve annealing each vacuum induction ingot.
  • the temperature is pre-heated to 600-800°C, and then at a rate of 5-45°C/h
  • the temperature is raised to 800-1000°C and kept for 4 ⁇ 32h, and then cooled to 600 ⁇ 800°C for 4 ⁇ 32h at a rate of 1 ⁇ 35°C/h, then air-cooled, and then polished and flat-headed to obtain the electroslag electrode.
  • the diameter of the resulting electroslag electrode should be matched with the diameter of the matching mold of the vacuum consumable electric arc furnace used in the vacuum consumable remelting step, that is, the diameter of the matching mold and the electrode should maintain an appropriate ratio, that is, filling
  • the ratio is about 0.8 to 0.9.
  • This application adopts the above solution to directly stress-relieve and anneal the vacuum induction ingot.
  • It can prevent the temperature from falling into the aging precipitation zone due to air cooling after the ingot is demolded in time to form excessive structural stress;
  • Reasonable heating rate increases the temperature of the steel ingot, aiming at the problem of low thermal conductivity of the superalloy, avoiding large thermal stress inside and outside the steel ingot;
  • keeping the temperature at 800 ⁇ 1000°C for a certain period of time can make the temperature of the steel ingot fully uniform and release the internal stress of solidification ;
  • Fourth, the slow cooling of 1 ⁇ 35°C/h and the heat preservation of 600 ⁇ 800°C for a certain time can effectively prevent the steel ingot from forming greater thermal stress and structural stress again.
  • the slag system used is (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag, (CaF 2 -CaO-Al 2 O 3- TiO 2 )
  • CaF 2 accounts for 60 to 75 wt%
  • CaO accounts for 10 to 25 wt%
  • Al 2 O 3 accounts for 8 to 13 wt%
  • TiO 2 accounts for 1 to 5 wt%.
  • electroslag The steady-state melting rate of remelting is controlled at 5-15kg/min, and before each electrode exchange, when the remaining weight of the current electrode is 500kg-1000kg, the steady-state melting rate will increase with a slope of 0.5-2kg/min.
  • the steady-state melting rate of electroslag remelting is controlled to be 5-15kg/min.
  • the subsequent adjustment of the melting rate before and after the electrode exchange can reasonably increase the molten pool when the electrode is exchanged.
  • the depth can solve the decrease of molten pool fluidity caused by the suspension of smelting during the electrode exchange process, reduce the disturbance of the molten pool caused by the instantaneous embedding of the electrode in the slag pool, and reduce the metallurgical quality problems such as inclusions and injection.
  • the demolded electroslag ingot is subjected to primary annealing, secondary annealing, forging and drawing to a predetermined size to obtain a consumable electrode.
  • the specific implementation method is as follows:
  • an annealing is started within 0.5-2h after demolding. Specifically, it is preheated to 300-550°C, held for 12-32h to achieve uniform temperature, and then heated at a rate of 1-25°C/h to 600 ⁇ Hold at 750°C for 4 ⁇ 32h, then heat up to 800 ⁇ 1000°C at a rate of 5 ⁇ 35°C/h and keep it at 800 ⁇ 1000°C for 4 ⁇ 32h, then cool to 550 ⁇ 750°C at a rate of 1 ⁇ 35°C/h and keep it at 4 ⁇ 32h, then Air cooling
  • the electroslag ingot after secondary annealing it is heated to 1100 ⁇ 1180°C before forging, and the heating time before forging is 4 ⁇ 12h.
  • the free forging adopts a fast forging machine of more than 3000 tons to draw the length in one direction, and each pass is pressed down on one side.
  • the amount is controlled at 5 ⁇ 30mm, and the final forging temperature is 850 ⁇ 1000°C;
  • the head and tail are flattened, and a consumable electrode is obtained.
  • the diameter of the primary consumable electrode should be matched with the diameter of the matching mold of the vacuum consumable arc furnace used in the primary vacuum consumable remelting.
  • the reason for adopting the above technical solution is that the obtained high-niobium superalloy ingots with a diameter of 1000mm or more in the electroslag ingots have great thermal stress during the solidification process and are very easy to burst; due to the reasonable requirements for consumable electrodes and corresponding crystallizers Filling ratio, the large-sized electroslag ingot cannot be directly used for one-time consumable remelting, and free forging is needed to reduce the diameter, for example, it can be 800-900mm; but because the diameter of the electroslag ingot is too large, solidification segregation Very serious, there are severe dendrite element segregation and low melting point phase between dendrites, and the thermoplasticity is extremely poor.
  • the application after the electroslag remelting is completed, is cooled by water in the water-cooled crystallizer in the adopted electroslag remelting furnace for 2-10 hours.
  • an annealing is started within 0.5-2h after demolding.
  • the first annealing preheat to 300 ⁇ 550°C to avoid excessive thermal stress caused by excessive temperature, then keep the temperature at 300 ⁇ 550°C for 12 ⁇ 32h to achieve uniform temperature, and then heat up to 600 at a rate of 1 ⁇ 25°C/h Keep it at ⁇ 750°C for 4 ⁇ 32h, then heat it up to 800 ⁇ 1000°C at a rate of 5 ⁇ 35°C/h and keep it for 4 ⁇ 32h, and then cool it at a rate of 1 ⁇ 35°C/h to 550 ⁇ 750°C and keep it for 4 ⁇ 32h, Then air-cooled.
  • the thermal stress formed by the temperature gradient during the solidification of the electroslag ingot can be released, and at the same time, the over-aging treatment is used to coarsen the strengthening phase to avoid the formation of structural stress, thereby inhibiting the direct explosion of the large-size superalloy electroslag ingot after demolding.
  • the electroslag ingots In order to improve the thermal plasticity of high-niobium superalloy electroslag ingots with a diameter of 800mm or more, the electroslag ingots should be subjected to secondary annealing after annealing, that is, high-temperature diffusion annealing. In order to avoid excessive thermal stress, the heating rate must be strictly controlled. Therefore, the electroslag ingot is kept at a temperature below 550-750°C for 4-24 hours, and then the temperature is raised to 800-1000°C at a rate of 5-35°C/h.
  • the steady-state melting rate is controlled to be 3.5-7.5kg/min; after 800-2000kg smelting is started, helium cooling is started; after the remaining 1500-5000kg, the current is reduced to adjust the melting rate to 3.0 ⁇ 7.0kg/min; after the remaining 200 ⁇ 1000kg, heat sealing is started to prepare a consumable remelted ingot.
  • the volume of the ingot will shrink during solidification, and there will be a gap with the mold wall.
  • the cooling water of the steel ingot and the outer wall of the mold cannot directly contact the cooling water to achieve heat dissipation.
  • Helium conducts heat; in the early stage of smelting, the steel ingot can dissipate heat through the bottom and the mold.
  • the heat dissipation at the bottom is limited. For this reason, it is necessary to pass in a proper amount of helium after a certain stage of smelting.
  • the primary consumable remelting ingot is first polished and flattened to obtain a diameter that matches the diameter of the crystallizer used in the secondary vacuum consumable remelting
  • the secondary consumable electrode when performing secondary vacuum consumable remelting, the steady-state melting rate is controlled to be 4.0 ⁇ 8.5kg/min; after smelting 1000 ⁇ 3000kg, it is cooled by helium gas; the current is reduced after the remaining 2000 ⁇ 5500kg Adjust the melting rate to 3.0 ⁇ 7.5kg/min; start heat sealing after the remaining 250 ⁇ 1500kg;
  • vacuum cooling is performed for 1 to 8 hours, and then stress relief annealing is started within 2 hours; during annealing, it is preheated to 300 to 750°C and kept for 4 to 32 hours to achieve uniform temperature. Then the temperature is raised to 800-1000°C at a rate of 5-50°C/h, kept for 4 to 32 hours, and then cooled to 550-750°C at a rate of 1 to 35°C/h for 4 to 32 hours, and then air-cooled.
  • this application will turn the primary consumable remelting ingots, flat head and tail to prepare secondary consumable electrodes, and then perform secondary consumable remelting. Since the diameter of the steel ingot after the secondary consumable remelting exceeds 800mm, there will be great thermal stress, so after the secondary consumable remelting is completed, vacuum cooling is required, and then the stress relief annealing is started within 2h to avoid the steel ingot. After demolding, it bursts.
  • annealing it should be preheated to 300 ⁇ 750°C and kept for 4 ⁇ 32h to achieve uniform temperature, then at a rate of 5 ⁇ 50°C/h to 800 ⁇ 1000°C and kept for 4 ⁇ 32h, and then at 1 ⁇ 35°C Cooling to 550 ⁇ 750°C for 4 ⁇ 32h at a rate of /h, and then air cooling.
  • the subsequent use of this method can release the thermal stress formed by the temperature gradient during the solidification of the consumable remelted ingot.
  • the over-aging treatment is used to make The strengthening phase is coarsened to avoid the formation of structural stress, thereby inhibiting the direct explosion of large-size superalloy electroslag ingots after demolding.
  • the method for preparing large-size, high-niobium, high-temperature 706 alloy provided by the present invention by reasonably controlling the amount of Al added in the molten steel, and adopting a specific quaternary slag system in the exchange electroslag remelting process, can make the process There is no Al and Ti elements and no obvious burning loss.
  • the present invention can break through the tonnage limit of induction furnace and atmosphere protection electroslag furnace, adopting conventional tonnage (such as 12 tons) vacuum induction furnace to prepare 2 electrodes, and then using electroslag furnace to exchange electrodes to smelt 2 induction ingots into 1 Electroslag ingots, which are then used to manufacture vacuum consumable ingots of at least 15 tons;
  • the electroslag furnace with limited tonnage of the electrode arm can be used to prepare 20-ton high-temperature alloy electroslag ingots by the method of exchange electroslag remelting;
  • Electroslag ingots prepared by exchange electroslag remelting are subjected to high temperature diffusion annealing to obtain a certain degree of thermoplasticity, and then free forging is used to open the billet to prepare a consumable electrode with a suitable diameter, which can significantly improve the melting stability of a consumable remelting process.
  • Sex
  • the secondary consumable electrode prepared by the primary consumable remelting steel ingot is used for the secondary consumable remelting. If necessary, further consumable remelting is performed multiple times, which can effectively solve the electroslag exchange during the electroslag remelting process.
  • Metallurgical defects such as inclusions at the ingot exchange electrode joints are used to prepare high-niobium superalloy consumable ingots with a diameter of 800mm or more and an ingot weight of more than 15 tons without metallurgical defects.
  • This embodiment is used to illustrate the method of preparing 706 alloy (a consumable ingot with a diameter of 1050 mm).
  • Target 706 alloy composition (by mass percentage):
  • the specific preparation method is as follows:
  • Vacuum induction smelting According to the designed alloy composition requirements, 50% of the return material is weighed according to the required elements of the alloy per unit weight, and the rest is made of new metal raw materials. Using a 12-ton vacuum induction furnace, the upper limit of the melting temperature is 1550°C. After melting, the composition of the molten steel is detected.
  • the content of Ni in the molten steel is controlled to be about 42.0wt%, the content of Nb is about 3.02wt%, and the content of Ti is about 1.80 wt%, Al content is about 0.30wt%; according to the amount of added metal material, refining is performed under electromagnetic stirring for 15-30 minutes, the refining temperature is 1350°C, and the tapping temperature is 1400°C. After pouring the steel, the furnace is cooled for 4 hours and then demolded to obtain two 12-ton vacuum electrode ingots with a diameter of 820 mm, which are then directly annealed.
  • the annealing furnace is preheated to 600°C, and then heated at a rate of 5°C/h to 800°C for 24 hours, and then cooled at a rate of 1°C/h to 600°C for 10 hours, and then air-cooled.
  • the annealed vacuum induction ingot car/polishing, flat head and tail are used to prepare the electroslag electrode.
  • Electroslag remelting The diameter of the crystallizer is 1100mm, and the slag system is (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag.
  • the specific composition is: CaF 2 60%, CaO 10%, Al 2 O 3 13% , TiO 2 10%.
  • the steady-state melting rate is 15kg/min, and Ar gas protection at a pressure of 0.2bar is introduced during the melting process to prevent the molten steel from contacting oxygen and nitrogen in the air during the melting process. Before the electrode exchange, when the remaining weight is 800kg, adjust the input power and voltage to increase the melting rate. On the basis of the steady-state melting rate, increase the melting rate with a slope of 1.05kg/min.
  • the electroslag electrode When it reaches 25kg/min, it will remain stable until the electroslag electrode is exchanged. .
  • the electrode exchange process maintains the smelting parameters before the exchange, and the exchange time cannot exceed 2 min.
  • the second electrode melts 100kg, the melting rate is increased by adjusting the input power and voltage, and the melting rate is reduced to 10kg/min at a slope of 0.50kg/min. After the second electrode remains 200kg, the heat sealing starts.
  • the water-cooled crystallizer in the furnace is cooled by water for 4 hours, and within 0.5 hours after demolding, it is transferred to the annealing furnace for stress relief annealing.
  • the annealing furnace should be pre-heated to 300°C, kept at 300°C for 12h, then at a rate of 5°C/h to 600°C for 4h, then at a rate of 10°C/h to 800°C for 5h, and then at 5°C/h Cool down to 600°C for 12 hours at a rate of h, then cool in air.
  • High temperature diffusion annealing of electroslag ingots install the furnace at a temperature below 550°C for 4 hours, then heat up to 800°C at a rate of 10°C/h, then heat up to 1050°C at a rate of 5°C/h, hold for 4 hours, and then heat at 5°C/h
  • the temperature was raised to 1150°C for 24 hours at a rate of h, and then cooled to 800°C for 32 hours at a rate of 5°C/h, and then air-cooled.
  • Electrode forging The heating temperature before forging of the electroslag ingot with a diameter of 1100mm is 1100°C, and the heating time before forging is 4h.
  • the free forging adopts a 3500 ton fast forging machine to draw length in one direction, and the unilateral reduction of each pass is controlled to 25mm, the final forging temperature is 850°C, and the final forging, turning, and flat head and tail are prepared to a diameter of 820mm. Extremely, used for a vacuum consumable remelting.
  • One-time vacuum consumable remelting The diameter of the crystallizer is 920mm, the consumable remelting is controlled by the melting rate, and the steady-state melting rate is controlled to 3.5kg/min; the helium cooling is started after 800kg of smelting; after the remaining 1500kg, the current is reduced to adjust the melting The speed reaches 3.0kg/min; after the remaining 200kg, the heat sealing is started, and the heat sealing is controlled by the current.
  • the primary consumable remelting ingot is machined and flat-headed to a diameter of 900mm, which is used for secondary vacuum consumable remelting.
  • Secondary vacuum self-consumption remelting 1050mm is used for the crystallizer, the melting is controlled by the melting rate, and the steady-state melting rate is controlled to 4.0kg/min; the helium cooling is started after the smelting of 1000kg; after the remaining 2000kg, the current is reduced to adjust the melting rate to 3.0 kg/min; after the remaining 250kg, the heat sealing is started, and the heat sealing is controlled by the current.
  • the secondary vacuum consumable remelting After the secondary vacuum consumable remelting is completed, it is vacuum cooled for 3 hours, and then the void is transferred to the annealing furnace for stress relief annealing within 2 hours to avoid the steel ingot from bursting after demolding.
  • the annealing furnace should be preheated to 300°C for 4 hours to achieve uniform temperature, then heated at a rate of 5°C/h to 800°C for 5 hours, and then cooled at a rate of 5°C/h to 550°C for 5 hours, and then air-cooled.
  • Test result The trial-produced 1050mm consumable ingot of 706 alloy weighs 15.5 tons, and there is no hot cracking, and no metallurgical defects such as black spots and white spots.
  • the composition test on the head and tail of the steel ingot showed that the Al and Ti elements at the head and tail have no obvious burning loss.
  • the Al element is 0.27% at the head and 0.24% at the tail.
  • the Ti element is 1.68% at the head and 1.78% at the tail.
  • This embodiment is used to illustrate the method of preparing 706 alloy (a consumable ingot with a diameter of 1050 mm).
  • Target 706 alloy composition (by mass percentage):
  • the specific preparation method is as follows:
  • Vacuum induction smelting According to the designed alloy composition requirements, 50% of the return material is weighed according to the required elements of the alloy per unit weight, and the rest is made of new metal raw materials. A 12-ton vacuum induction furnace is used. The upper limit of the melting temperature is 1550°C. After melting, the composition of the molten steel is detected. By adding new metal, the content of Ni in the molten steel is controlled to be about 42.5% by weight, the content of Nb is about 2.92% by weight, and the content of Ti is about 1.65. wt%, Al content is about 0.22wt%, refining under electromagnetic stirring for 40 minutes, the refining temperature is 1480°C, and the tapping temperature is 1500°C. The steel was poured in two times.
  • the furnace was cooled for 4 hours and then demolded to obtain two 12-ton consumable ingots with a diameter of 820mm, which were then directly annealed.
  • the annealing furnace is preheated to 650°C, and then heated to 900°C at a rate of 25°C/h for 24 hours, and then cooled to 700°C at a rate of 15°C/h for 10 hours, and then air-cooled.
  • the annealed vacuum induction ingots are turned and flattened to prepare electroslag electrodes.
  • Electroslag remelting The diameter of the crystallizer is 1100mm, and the slag system is (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag.
  • the specific composition is: CaF 2 64%, CaO 15%, Al 2 O 3 10 %, TiO 2 6%.
  • the steady-state melting rate is 10kg/min, and Ar gas protection at 0.2bar pressure is introduced during the smelting process to prevent the molten steel from contacting oxygen and nitrogen in the air during the smelting process.
  • Ar gas protection at 0.2bar pressure is introduced during the smelting process to prevent the molten steel from contacting oxygen and nitrogen in the air during the smelting process.
  • the remaining weight is 500kg, adjust the input power and voltage to increase the melting rate, and increase the melting rate with a slope of 0.75kg/min on the basis of the steady-state melting rate.
  • the electroslag electrode When it reaches 12kg/min, it remains stable until the electroslag electrode is exchanged. .
  • the electrode exchange process maintains the smelting parameters before the exchange, and the exchange time cannot exceed 2 min.
  • the second electrode melts 300kg, the melting rate is increased by adjusting the input power and voltage, and the melting rate is reduced to 6kg/min at a slope of 1.5kg/min. After the second electrode is left with 500kg, the heat sealing starts.
  • the water-cooled crystallizer in the furnace is cooled by water for 4 hours, and after demolding, it is transferred to the annealing furnace for stress relief annealing within 2 hours.
  • the annealing furnace should be preheated to 350°C, kept at 350°C for 24h, then at a rate of 20°C/h to 650°C for 30h, then at a rate of 25°C/h to 900°C for 72h, and then at 30°C/h Cool down to 550°C for 32 hours at a rate of h, then cool in air.
  • High temperature diffusion annealing of electroslag ingots install the furnace at a temperature below 550°C for 4 hours, then heat up to 1000°C at a rate of 15°C/h, then heat up to 1150°C at a rate of 25°C/h, hold for 12 hours, and then hold at 25°C/h The temperature was raised to 1250°C for 72 hours at a rate of h, and then cooled to 950°C at a rate of 35°C/h for 8 hours, and then air-cooled.
  • Electrode forging The heating temperature before forging of the electroslag ingot with a diameter of 1100mm is 1180°C, and the heating time before forging is 12h. Free forging adopts 3500 ton fast forging machine to draw length in one direction, the single side reduction of each pass is controlled to 30mm, the final forging temperature is 1000°C, and the final forging, turning, and flat head and tail are prepared to a diameter of 820mm. Extremely, used for a vacuum consumable remelting.
  • One-time vacuum consumable remelting The diameter of the crystallizer is 920mm, and the consumable remelting is controlled by the melting rate.
  • the steady-state melting rate is controlled to 7.5kg/min; the helium cooling is started after 1800kg of smelting; after the remaining 5000kg, the current is reduced and the melting is adjusted.
  • the speed reaches 7.0kg/min; after the remaining 1500kg, the heat sealing is started, and the heat sealing is controlled by the current.
  • the primary consumable remelting ingot is machined and flat-headed to a diameter of 900mm, which is used for secondary vacuum consumable remelting.
  • Secondary vacuum self-consumption remelting 1050mm is selected for the crystallizer, the melting is controlled by the melting rate, and the steady-state melting rate is controlled at 8.5kg/min; after 3000kg of smelting starts, helium cooling is started; after the remaining 5500kg, the current is reduced to adjust the melting rate to 7.5 kg/min; after the remaining 1500kg, the heat sealing is started, and the heat sealing is controlled by the current.
  • the secondary vacuum consumable remelting After the secondary vacuum consumable remelting is completed, it is vacuum cooled for 8 hours, and then the void is transferred to the annealing furnace for stress relief annealing within 2 hours to prevent the steel ingot from bursting after demoulding.
  • the annealing furnace should be preheated to 750°C for 32 hours to achieve uniform temperature, and then heated at a rate of 35°C/h to 1000°C for 32 hours, and then cooled at a rate of 25°C/h to 750°C for 32 hours, and then air-cooled to achieve the target Ingot casting.
  • Test result The trial-produced 1050mm consumable ingot of 706 alloy weighs 15.5 tons, and there is no hot cracking, and no metallurgical defects such as black spots and white spots.
  • the composition test on the head and tail of the steel ingots shows that there is no obvious burning loss of Al and Ti elements at the head and tail.
  • Al element is 0.24% for the head and 0.19% for the tail
  • Ti element is 1.68% for the head and 1.50 for the tail. %.
  • This embodiment is used to illustrate the method of preparing 706 alloy (a consumable ingot with a diameter of 1050 mm).
  • Target 706 alloy composition (by mass percentage):
  • the specific preparation method is as follows:
  • Vacuum induction smelting According to the designed alloy composition requirements, 60% of the return material is weighed according to the required elements of the alloy per unit weight, and the rest is made of new metal raw materials. A 12-ton vacuum induction furnace is used. The upper limit of the melting temperature is 1350°C. After melting, the composition of the molten steel is detected. By adding new metal, the content of Ni in the molten steel is controlled to be about 40.5wt%, the content of Nb is about 3.2wt%, and the content of Ti is about 1.57 wt%, Al content is about 0.15wt%, refining under electromagnetic stirring for 100 minutes, the refining temperature is 1400°C, and the tapping temperature is 1450°C. The steel was poured in two times.
  • the furnace was cooled for 4 hours and then demolded to obtain two 12-ton consumable ingots with a diameter of 820mm, which were then directly annealed.
  • the annealing furnace is pre-heated to 750°C, and then heated to 1000°C at a rate of 40°C/h for 24 hours, then cooled to 800°C at a rate of 30°C/h for 30 hours, and then air-cooled.
  • the annealed vacuum induction ingots are turned and flattened to prepare electroslag electrodes.
  • Electroslag remelting The diameter of the crystallizer is 1100mm, and the slag system is (CaF2-CaO-Al2O3-TiO2) quaternary slag.
  • the specific composition is: CaF264%, CaO 15%, Al2O3 8%, TiO2 1%.
  • the steady-state melting rate is 5kg/min, and Ar gas protection at 0.2bar pressure is introduced during the smelting process to prevent the molten steel from contacting oxygen and nitrogen in the air during the smelting process.
  • the electrode exchange Before the electrode exchange, when the remaining weight is 600kg, adjust the input power and voltage to increase the melting rate. On the basis of the steady-state melting rate, increase the melting rate with a slope of 2kg/min. When it reaches 20kg/min, it will remain stable until the electroslag electrode is exchanged. The electrode exchange process maintains the smelting parameters before the exchange, and the exchange time cannot exceed 2 min. After the electrode exchange is completed, after the second electrode melts 500kg, the melting rate is increased by adjusting the input power and voltage, and the melting rate is reduced to 15kg/min at a slope of 2kg/min. When the second electrode remains 500kg, the heat sealing starts.
  • the water-cooled crystallizer in the furnace is cooled by water for 4 hours, and the mold is transferred to the annealing furnace for stress relief annealing within 1 hour.
  • the annealing furnace should be preheated to 550°C, kept at 400°C for 24h, then at a rate of 15°C/h to 750°C for 24h, then at a rate of 18°C/h to 1000°C for 36h, and then at 15°C/h It is cooled to 750°C for 12 hours at a rate of h, and then air-cooled.
  • High temperature diffusion annealing of electroslag ingots install the furnace at a temperature below 550°C for 4 hours, then heat up to 950°C at a rate of 10°C/h, then heat up to 1100°C at a rate of 15°C/h, hold for 12 hours, and then at 20°C/h The temperature was raised to 1200°C for 48 hours at a rate of h, and then cooled to 850°C at a rate of 15°C/h for 24 hours, and then air-cooled.
  • Electrode forging The heating temperature before forging of the electroslag ingot with a diameter of 1100mm is 1150°C, and the heating time before forging is 8h.
  • the free forging adopts a 3500 tons fast forging machine to draw length in one direction, and the unilateral reduction of each pass is controlled to 5mm, and the final forging temperature is 900°C.
  • the final forging, turning, and flat head and tail are prepared to a diameter of 820mm. Extremely, used for a vacuum consumable remelting.
  • One-time vacuum consumable remelting The diameter of the crystallizer is 920mm, the consumable remelting is controlled by the melting rate, and the steady-state melting rate is controlled to 5.0kg/min; the helium cooling is started after 1500kg is melted; the current is reduced after the remaining 2000kg to adjust the melting The speed reaches 6.0kg/min; after the remaining 250kg, the heat sealing is started, and the heat sealing is controlled by the current.
  • the primary consumable remelting ingot is machined and flat-headed to a diameter of 900mm, which is used for secondary vacuum consumable remelting.
  • Secondary vacuum self-consumption remelting The mold is 1050mm, the melting is controlled by the melting rate, and the steady-state melting rate is controlled to 6.5kg/min; the helium cooling is started after 1500kg is melted; the current is reduced after the remaining 3000kg to adjust the melting rate to 6.0 kg/min; after the remaining 1000kg, the heat sealing is started, and the heat sealing is controlled by the current.
  • vacuum cooling is performed for 5 hours, and then the void is transferred to the annealing furnace for stress relief annealing within 2 hours to prevent the ingot from bursting after demolding.
  • the annealing furnace should be preheated to 450°C for 24 hours to achieve uniform temperature, then heated at a rate of 25°C/h to 900°C for 24 hours, and then cooled at a rate of 35°C/h to 600°C for 12 hours, and then air-cooled to achieve the target Ingot casting.
  • Test results The trial-produced 1050mm consumable ingot of 706 alloy weighs 15.8 tons. There is no hot cracking and no metallurgical defects such as black spots and white spots.
  • the composition test on the head and tail of the steel ingots shows that there is no obvious burning loss of Al and Ti elements at the head and tail.
  • the Al element is 0.16% for the head and 0.12% for the tail.
  • the Ti element is 1.60% for the head and 1.46 for the tail. %.
  • the comparative example is used to illustrate the preparation method of 706 alloy (a consumable ingot with a diameter of 920 mm) prepared by a triple preparation process.
  • the target 706 alloy composition is the same as the 706 alloy composition of Example 1 (by mass percentage):
  • the specific preparation method is as follows:
  • Vacuum induction smelting According to the designed alloy composition requirements, 40% of the return material is weighed according to the required elements of the alloy per unit weight, and the rest is made of new metal raw materials. A 12-ton vacuum induction furnace is used to prepare two 12-ton consumable ingots with a diameter of 820mm. The upper melting temperature is 1550°C. After melting, the composition of the molten steel is detected. By adding new metal, the content of Ni in the molten steel is controlled to about 42.0wt%. The Nb content is about 3.10wt%, the Ti content is about 1.82wt%, and the Al content is about 0.35wt%.
  • Electromagnetic stirring is used for 40 minutes; the refining temperature is 1480°C, and the tapping temperature is 1500°C.
  • the furnace is cooled for 4 hours and then demoulded, and then directly subjected to annealing treatment.
  • the annealing furnace is preheated to 650°C, and then heated to 900°C at a rate of 25°C/h for 24 hours, and then cooled to 600°C at a rate of 15°C/h for 10 hours, and then air-cooled.
  • the annealed vacuum induction ingots are turned, and the ends are flattened to prepare electroslag electrodes.
  • Electroslag remelting The diameter of the crystallizer is 1100mm, and the slag system is (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag.
  • the specific composition is: CaF 2 70%, CaO 15% , Al 2 O 3 15% , TiO 2 6%.
  • the steady-state melting rate is 10kg/min, and Ar gas protection at 0.2bar pressure is introduced during the smelting process to prevent the molten steel from contacting oxygen and nitrogen in the air during the smelting process.
  • Ar gas protection at 0.2bar pressure is introduced during the smelting process to prevent the molten steel from contacting oxygen and nitrogen in the air during the smelting process.
  • the remaining weight is 600kg, adjust the input power and voltage to increase the melting rate, and increase the melting rate with a slope of 0.55kg/min on the basis of the steady-state melting rate.
  • the electroslag electrode When it reaches 15kg/min, it will remain stable until the electroslag electrode is exchanged. .
  • the electrode exchange process maintains the smelting parameters before the exchange, and the exchange time cannot exceed 2 min.
  • the second electrode melts 200kg, the melting rate is increased by adjusting the input power and voltage, and the melting rate is reduced to 10kg/min at a slope of 0.75kg/min.
  • the second electrode remains 500kg, the heat sealing starts.
  • the electroslag remelting After the electroslag remelting is completed, it should be cooled by passing water in a water-cooled crystallizer in the furnace for 4 hours, and transferred to the annealing furnace for stress relief annealing within 0.5 hours after demolding.
  • the annealing furnace should be preheated to 450°C, kept at 450°C for 24h, then at a rate of 15°C/h to 650°C for 4h, then at a rate of 25°C/h to 950°C for 12h, and then at 15°C/h Cool down to 600°C for 12 hours at a rate of h, then cool in air.
  • High temperature diffusion annealing of electroslag ingots install the furnace at a temperature below 550°C for 4 hours, then heat up to 950°C at a rate of 10°C/h, then heat up to 1100°C at a rate of 15°C/h, hold for 12 hours, and then at 20°C/h The temperature was raised to 1190°C for 48 hours at a rate of h, and then cooled to 850°C for 24 hours at a rate of 15°C/h, and then air-cooled.
  • Electrode forging The heating temperature before forging of the electroslag ingot with a diameter of 1100mm is 1150°C, and the heating time before forging is 10h.
  • the free forging adopts a 3500 ton fast forging machine to draw the length in one direction.
  • the unilateral reduction of each pass is controlled to 25mm, and the final forging temperature is 900°C.
  • the consumable electrode with a diameter of 820mm is finally prepared by forging, turning, and flat head. .
  • Self-consumable remelting The diameter of the crystallizer is 920mm, and the self-consumable remelting is controlled by the melting rate.
  • the steady-state melting rate is controlled at 5.5kg/min; the helium cooling is started after the smelting of 1000kg; after the remaining 2000kg, the current is reduced to adjust the melting rate to 4.0kg/min; after the remaining 500kg, the heat sealing is started, and the heat sealing is controlled by the current.
  • the consumable remelting After the consumable remelting is completed, it is cooled in vacuum for 3 hours, and then the void is transferred to the annealing furnace for stress relief annealing within 2 hours to prevent the ingot from bursting after demoulding.
  • the annealing furnace should be preheated to 450°C for 8 hours to achieve uniform temperature, and then heated at a rate of 10°C/h to 850°C for 24 hours, and then cooled at a rate of 15°C/h to 600°C for 12 hours, and then air-cooled.
  • Test results 706 alloy 920mm consumable ingots trial-produced by the triple smelting process, weighing 15.2 tons, and no hot cracking; the composition test on the head and tail of the steel ingot, the test results show that the head and tail Al and Ti elements burned significantly, and Al The element is 0.29% in the head and 0.19% in the tail, and the Ti element is 1.62% in the head and 1.80% in the tail.
  • the secondary consumable ingot with a diameter of 920mm is homogenized, diffused and annealed at high temperature, it is polished and forged to prepare forged bars. The bars were inspected by non-destructive flaw detection, and abnormal signals were found at the electroslag remelting joints, and an obvious black spot defect was found at the joints after anatomy.

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Abstract

Provided are a large-size high-niobium and high-temperature 706 alloy ingot and a smelting process thereof, wherein the smelting process includes: vacuum induction smelting to obtain multiple vacuum induction ingots with the same composition, then the same number of electroslag electrodes are prepared, using (CaF 2-CaO-Al 2O 3-TiO 2) quaternary slag to exchange electroslag remelting, using the obtained electroslag ingot to obtain consumable electrode, then using the consumable electrode as the starting material to perform two vacuum consumable remelting. This process can be used to prepare large-size ingots of high-niobium and high-temperature 706 alloy with an ingot weight of more than 15 tons and a diameter of more than 800 mm, minimizing the formation of black spots and white spots metallurgical defects, and reducing the burning rate of Al and Ti elements.

Description

一种大尺寸高铌高温706合金铸锭及其冶炼工艺Large-size high-niobium high-temperature 706 alloy ingot and smelting process 技术领域Technical field
本发明涉及大尺寸高铌合金技术领域,更具体地说,它涉及一种大尺寸高铌高温706合金铸锭及其冶炼工艺。The invention relates to the technical field of large-size high-niobium alloys, and more specifically, it relates to a large-size high-niobium high-temperature 706 alloy ingot and its smelting process.
背景技术Background technique
706高温合金是一种特殊的合金,其通过在原料中中加入与基体金属原子(如镍)尺寸不同的元素(铬、钨、钼等),引起基体金属点阵的畸变,通过加入能降低合金基体堆垛层错能的元素(如钴)和加入能减缓基体元素扩散速率的元素(钨、钼等),以强化基体。钢锭通过时效处理,可从过饱和固溶体中析出第二相(γ′、γ"、碳化物等),以强化合金。γ′相结构与基体相同,均为面心立方结构,点阵常数与基体相近,并与晶体共格,因此γ′相在基体中能呈细小颗粒状均匀析出,阻碍位错运动,而产生显著的强化作用。γ′相是A3B型金属间化合物,A代表镍、钴,B代表铝、钛、铌、钽、钒、钨,而铬、钼、铁既可为A又可为B。镍基合金中典型的γ′相为Ni3(Al,Ti),γ"相为体心四方结构,其组成为Ni3Nb,因γ"相与基体的错配度较大,能引起较大程度的共格畸变,使合金获得很高的屈服强度,但超过700℃,强化效应便明显降低,需要采用特殊处理工艺进行处理。并且,对于含Al、Ti元素的706合金,电渣重熔过程易出现Al、Ti元素的烧损,这也是制备过程中亟待解决的问题。706 superalloy is a special alloy. By adding elements (chromium, tungsten, molybdenum, etc.) different in size from the base metal atoms (such as nickel) in the raw material, it causes the distortion of the base metal lattice, which can be reduced by adding Alloy matrix stacking fault energy elements (such as cobalt) and adding elements that can slow down the diffusion rate of matrix elements (tungsten, molybdenum, etc.) to strengthen the matrix. Through the aging treatment, the second phase (γ', γ", carbide, etc.) can be precipitated from the supersaturated solid solution in the steel ingot to strengthen the alloy. The structure of the γ'phase is the same as that of the matrix, which is a face-centered cubic structure, and the lattice constant is The matrix is similar and coherent with the crystal, so the γ'phase can be uniformly precipitated in the matrix in the form of fine particles, which hinders the movement of dislocations and produces a significant strengthening effect. The γ'phase is an A3B type intermetallic compound, and A represents nickel, Cobalt, B represents aluminum, titanium, niobium, tantalum, vanadium, and tungsten, while chromium, molybdenum, and iron can be either A or B. The typical γ'phase in nickel-based alloys is Ni3(Al, Ti), γ" The phase is a body-centered tetragonal structure, and its composition is Ni3Nb. Because the mismatch between the γ" phase and the matrix is large, it can cause a large degree of coherent distortion, so that the alloy can obtain a high yield strength, but when it exceeds 700 ℃, it is strengthened. The effect is significantly reduced, and special treatment processes are required. Moreover, for the 706 alloy containing Al and Ti elements, the burning of Al and Ti elements is prone to occur during the electroslag remelting process, which is also an urgent problem to be solved in the preparation process.
此外,对于Nb含量超过3%的高温镍基706合金,欧美生产10吨以上的高温大锭型普遍采用“真空感应熔炼+电渣重熔+真空自耗重熔”的三联冶炼工艺。例如,专利US 20020170386A1给出了一种合金直径762mm以上大锭型的三联冶炼工艺。这种三联冶炼设备使用过程中,锭型和电极的直径需要进行匹配,专利中给出了几种锭型和电极的匹配例子。但是,对于重量超过15吨的高温合金自耗锭,考虑到三联冶炼环节间的损耗(电极车光和平头尾),真空感应锭的重量超过20吨,对真空感应炉和电渣重熔炉的设备能力要求更高。而目前国内生产15吨以上高温合金大锭型的主要技术瓶颈在于,没有公称容量大于20吨级的真空感应熔炼装备,无法制备20吨级以上的单支真空感应电极锭坯。为了解决此问题,适应国内设备情况,只能采用真空感应炉浇注2支10吨级的感应锭,再利用双支臂交换电极重熔,用两个小吨位的短电极制备大吨位的高温合金电渣 锭,再通过锻制电极用于后续的真空自耗重熔。然而,采用双支臂交换电极重熔的方法制备大尺寸电渣锭,在电极交换过程中容易形成接注、流钢、成分波动和夹杂等一系列的质量缺陷,即使通过后续的高温扩散退火和电极锻制也无法完全消除上述质量缺陷。在随后的真空自耗重熔过程中,当熔炼至电极接头处时,上述质量缺陷会造成自耗重熔工艺冶炼参数出现波动,而合金化程度高的706合金对自耗重熔冶炼工艺参数十分敏感,参数波动极易产生黑斑、白斑等冶炼缺陷,进而影响自耗锭的冶金质量。In addition, for the high-temperature nickel-based 706 alloy with a Nb content of more than 3%, the triple smelting process of "vacuum induction melting + electroslag remelting + vacuum consumable remelting" is generally used for high-temperature large ingots of more than 10 tons produced in Europe and the United States. For example, the patent US20020170386A1 provides a triple smelting process for large ingots with an alloy diameter of 762 mm or more. During the use of this triple smelting equipment, the diameter of the ingot type and the electrode needs to be matched. The patent provides several examples of the matching of the ingot type and the electrode. However, for superalloy consumable ingots weighing more than 15 tons, taking into account the loss between the triple smelting process (electrode car light and flat head and tail), the weight of vacuum induction ingots exceeds 20 tons, which is suitable for vacuum induction furnaces and electroslag remelting furnaces. The equipment capacity is more demanding. At present, the main technical bottleneck for domestic production of large ingots of high-temperature alloys of more than 15 tons is that there is no vacuum induction melting equipment with a nominal capacity of more than 20 tons, and it is impossible to prepare a single vacuum induction electrode ingot of more than 20 tons. In order to solve this problem and adapt to the domestic equipment situation, only two 10-ton induction ingots can be poured in a vacuum induction furnace, and then remelted using double-arm exchange electrodes, and two small-tonnage short electrodes are used to prepare large-tonnage high-temperature alloys. Electroslag ingots are then used for subsequent vacuum consumable remelting through forged electrodes. However, the double-arm exchange electrode remelting method is used to prepare large-size electroslag ingots, and a series of quality defects such as injection, flow steel, composition fluctuation and inclusions are easily formed during the electrode exchange process, even through the subsequent high-temperature diffusion annealing. And electrode forging can not completely eliminate the above-mentioned quality defects. In the subsequent vacuum consumable remelting process, when smelted to the electrode joint, the above-mentioned quality defects will cause the consumable remelting process smelting parameters to fluctuate, and the 706 alloy with a high degree of alloying affects the consumable remelting smelting process parameters Very sensitive, parameter fluctuations are prone to smelting defects such as black spots and white spots, which will affect the metallurgical quality of consumable ingots.
发明内容Summary of the invention
针对现有技术存在的不足,本发明的第一个目的在于提供一种大尺寸高铌高温706合金铸锭,所得铸锭重量至少可达15吨,且无黑斑、白斑等冶金缺陷,Al、Ti元素无明显烧损,采用该铸锭所锻造的棒材,经无损探伤检验,发现电渣重熔接头处无异常信号。In view of the shortcomings of the prior art, the first object of the present invention is to provide a large-size high-niobium high-temperature 706 alloy ingot, the weight of the obtained ingot can reach at least 15 tons, and there is no metallurgical defects such as black spots and white spots. , Ti element has no obvious burning loss. The bar forged from the ingot has been inspected by non-destructive flaw detection, and it is found that there is no abnormal signal at the electroslag remelting joint.
本发明的第二个目的在于提供上述大尺寸高铌高温706合金铸锭的冶炼工艺,其实现锭重15吨以上、直径800mm以上的高铌高温合金大尺寸铸锭的冶炼,冶炼过程Al、Ti元素无明显烧损,能有效预防热裂问题,最大限度地抑制黑斑和白斑冶金缺陷形成,降低元素偏析程度,提高钢锭的热塑性。The second object of the present invention is to provide a smelting process for the above-mentioned large-size high-niobium high-temperature 706 alloy ingots, which realizes the smelting of large-size high-niobium high-temperature alloy ingots with an ingot weight of 15 tons or more and a diameter of 800 mm or more. The smelting process is Al, Ti element has no obvious burning loss, can effectively prevent the problem of hot cracking, minimize the formation of black and white metallurgical defects, reduce the degree of element segregation, and improve the thermoplasticity of the steel ingot.
为实现上述目的,本发明提供了如下技术方案:一种大尺寸高铌高温706合金铸锭,其特征在于,所述高铌高温合金大尺寸铸锭为直径在800mm以上,按质量百分比计,所述大尺寸高铌高温706合金铸锭的化学成分为:In order to achieve the above objective, the present invention provides the following technical solution: a large-size high-niobium high-temperature 706 alloy ingot, characterized in that the high-niobium high-temperature alloy large-size ingot has a diameter of 800mm or more, and is calculated by mass percentage. The chemical composition of the large-size high-niobium high-temperature 706 alloy ingot is:
C≤0.02wt%,Cr 15.5~16.5wt%,Ni 40.0~43.0wt%,Nb 2.8~3.2wt%,Ti 1.5~1.8wt%,Al 0.1~0.3wt%,Si≤0.10wt%,Mn≤0.20wt%,P≤0.015wt%,S≤0.0013wt%,Co≤0.30wt%,Mo≤0.20wt%,B≤0.006wt%,Cu≤0.30wt%,Ca≤0.005wt%,N≤0.006wt%,O≤0.005wt%,Fe余量。C≤0.02wt%, Cr 15.5~16.5wt%, Ni 40.0~43.0wt%, Nb 2.8~3.2wt%, Ti 1.5~1.8wt%, Al 0.1~0.3wt%, Si≤0.10wt%, Mn≤0.20 wt%, P≤0.015wt%, S≤0.0013wt%, Co≤0.30wt%, Mo≤0.20wt%, B≤0.006wt%, Cu≤0.30wt%, Ca≤0.005wt%, N≤0.006wt% , O≤0.005wt%, Fe balance.
本发明提供的一种大尺寸高铌高温706合金铸锭的冶炼工艺,包括以下步骤:The smelting process of large-size high-niobium high-temperature 706 alloy ingot provided by the present invention includes the following steps:
真空感应熔炼:根据设计的合金成分要求,按单位重量的合金所需元素称取纯金属原材料和/或返回料为原料,进行真空感应熔炼,控制熔炼母液中Ni含量为40.0~43.0wt%,Nb含量为2.80~3.3wt%,Ti含量为0.5~2.0wt%,Al含量为0.2~0.5wt%,浇注多支成分相同的真空感应锭;Vacuum induction smelting: According to the designed alloy composition requirements, the pure metal raw materials and/or return materials are weighed according to the required elements of the alloy per unit weight as raw materials, and vacuum induction smelting is performed to control the Ni content in the smelting mother liquor to 40.0-43.0wt%. Nb content is 2.80~3.3wt%, Ti content is 0.5~2.0wt%, Al content is 0.2~0.5wt%, and multiple vacuum induction ingots with the same composition are poured;
交换电渣重熔:利用所制成的真空感应锭制得相同数量的电渣电极;采用所有制得的电渣电极,氩气保护状态下进行交换电渣重熔,所采用的渣系为(CaF 2-CaO-Al 2O 3-TiO 2)四元渣,(CaF 2-CaO-Al 2O 3-TiO 2)四元渣中CaF 2占60~75wt%,CaO占10~25wt%,Al 2O 3占8~13wt%,TiO 2占1~10wt%;交换电渣重熔结束后,冷却,脱模,制得电渣锭: Exchange electroslag remelting: the same number of electroslag electrodes are prepared by using the vacuum induction ingots made; all the prepared electroslag electrodes are used, and the exchange electroslag remelting is performed under argon protection. The slag system used is ( CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag, (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag contains 60~75wt% of CaF 2 and 10~25wt% of CaO. Al 2 O 3 accounts for 8 to 13 wt%, and TiO 2 accounts for 1 to 10 wt%; after the exchange electroslag remelting is completed, it is cooled and demolded to obtain an electroslag ingot:
一次真空自耗重熔:对脱模的电渣锭进行一次退火、二次退火、锻造拔长至预定尺寸,制得一次自耗电极,其中二次退火温度高于一次退火温度;然后利用一次自耗电极进行一次真空自耗重熔;Primary vacuum consumable remelting: the demolded electroslag ingot is subjected to primary annealing, secondary annealing, forging and drawing to a predetermined size to obtain a primary consumable electrode, wherein the secondary annealing temperature is higher than the primary annealing temperature; then use A consumable electrode is remelted once in vacuum;
二次真空自耗重熔:对一次真空自耗重熔所得的一次自耗重熔锭,车光、平头尾,得到二次自耗电极;然后利用二次自耗电极进行二次真空自耗重熔,制备目标直径的铸锭Secondary vacuum consumable remelting: the primary consumable remelted ingots obtained by the primary vacuum consumable remelting, car light, flat head and tail, to obtain a secondary consumable electrode; then use the secondary consumable electrode for secondary vacuum Consumable remelting to prepare ingots of target diameter
在本发明的上述技术方案中,为了克服Al、Ti的烧损问题,控制熔炼母液中Al含量在0.2~0.5wt%之间,可在一定程度上利用额外加入的Al作为脱氧剂,并在电渣重熔过程中采用了(CaF 2-CaO-Al 2O 3-TiO 2)四元渣且(CaF 2-CaO-Al 2O 3-TiO 2)四元渣中CaF 2占60~75wt%,CaO占10~25wt%,Al 2O 3占8~13wt%,TiO 2占1~10wt%,根据额外加入的Al的量,合理设计渣系中各部分的组成,尤其TiO 2的含量,将渣系中TiO 2的含量控制为1~10wt%,可解决电渣锭头尾Ti元素的烧损问题,也可保证电渣锭中Ti成分均匀,并可最大程度地减少易氧化元素的烧损;为了克服真空感应熔炼装备容量不足的问题,采用常规吨位(如12吨)的真空感应炉制备多支成分相同的感应锭(这样也降低了对单支感应锭重量的要求),从而制备多支电渣电极,然后采用电极交换重熔,制备大吨位的电渣锭,然后进行两次真空自耗重熔,其中,通过一次真空自耗重熔,可改善电极交换接头处的冶金质量,再通过二次真空自耗重熔,可彻底解决冶金质量问题,从而制备处高质量的、无冶金缺陷的至少达15吨级的高温合金大尺寸自耗锭。考虑到损耗,多支真空感应锭的重量之和应是铸锭目标重量的125%~160%。 In the above technical scheme of the present invention, in order to overcome the burning loss of Al and Ti, the Al content in the smelting mother liquor is controlled to be between 0.2 and 0.5 wt%, and the additional Al can be used as a deoxidizer to a certain extent, and remelting process using (CaF 2 -CaO-Al 2 O 3 -TiO 2) and four yuan slag (CaF 2 -CaO-Al 2 O 3 -TiO 2) four yuan CaF 2 slag accounts for 60 ~ 75wt %, CaO accounts for 10-25wt%, Al 2 O 3 accounts for 8-13wt%, TiO 2 accounts for 1-10wt%. According to the amount of additional Al added, the composition of each part of the slag system, especially the content of TiO 2 , The content of TiO 2 in the slag system is controlled to 1-10wt%, which can solve the burning problem of Ti element at the head and tail of the electroslag ingot, and also ensure the uniformity of the Ti composition in the electroslag ingot, and minimize the easily oxidized elements In order to overcome the problem of insufficient capacity of vacuum induction melting equipment, a conventional tonnage (such as 12 tons) vacuum induction furnace is used to prepare multiple induction ingots with the same composition (this also reduces the requirement for the weight of a single induction ingot), In this way, a plurality of electroslag electrodes are prepared, and then electrode exchange remelting is used to prepare large-tonnage electroslag ingots, and then two vacuum consumable remeltings are carried out. Among them, one vacuum consumable remelting can improve the electrode exchange joint. Metallurgical quality, and then through secondary vacuum consumable remelting, can completely solve the metallurgical quality problem, so as to prepare high-quality, non-metallurgical defects of at least 15 tons of high-temperature alloy large-size consumable ingot. Considering the loss, the total weight of multiple vacuum induction ingots should be 125% to 160% of the target weight of the ingot.
在优选的实施方案中,真空感应熔炼步骤中,熔化温度为1300~1550℃,原料熔清后,在电磁搅拌作用下精炼15~120min,精炼温度为1350~1550℃;然后冷却1~10小时后,脱模,得真空感应锭;重复多次该真空感应熔炼过程,得多支成分相同的真空感应锭。In a preferred embodiment, in the vacuum induction melting step, the melting temperature is 1300-1550°C. After the raw materials are melted, refining is carried out under electromagnetic stirring for 15-120 minutes, and the refining temperature is 1350-1550°C; then cooling for 1-10 hours After that, the mold is demolded to obtain a vacuum induction ingot; the vacuum induction smelting process is repeated many times, and there are many vacuum induction ingots with the same composition.
事实上,当真空感应锭直径超过800mm,单支重量超过10吨时,对于高铌的高温合金大尺寸感应锭在浇铸完成后的凝固过程中会产生很大的热应力,尤其是含Al、Ti的时效析出型合金,在冷却至强化型时效析出温度范围后,会析出强化相造成更大的组织应力,严重时会导致钢锭直接炸裂。但是脱模时间过短,钢锭未完全凝固,过早脱模易开裂。In fact, when the diameter of the vacuum induction ingot exceeds 800mm and the single weight exceeds 10 tons, large-size induction ingots of high-niobium superalloys will produce great thermal stress during the solidification process after casting, especially those containing Al, Ti aging precipitation alloys, after being cooled to the enhanced aging precipitation temperature range, will precipitate strengthening phases and cause greater structural stress, and in severe cases, the steel ingot will burst directly. However, if the demolding time is too short, the steel ingot is not completely solidified, and premature demolding is easy to crack.
为此,在优选的实施方案中,制备电渣电极的方式为,对每支真空感应锭直接去应力退火,退火时,预先升温至600~800℃,而后以5~45℃/h的速度升温至800~1000℃并保温4~32h,而后以1~35℃/h的速度冷却至600~800℃保温4~32h,而后空冷,然后再车光、平头尾,即得电渣电极。通常,所得电渣电极的直径应与对应真空自耗重熔步骤所用真空自耗电弧炉的配套结晶器的直径相适配,即配套结晶器与电极的直径应保持一个合适比例,即充填比,约为0.8~0.9。For this reason, in a preferred embodiment, the method of preparing the electroslag electrode is to directly stress-relieve annealing each vacuum induction ingot. During annealing, the temperature is pre-heated to 600-800°C, and then at a rate of 5-45°C/h The temperature is raised to 800-1000℃ and kept for 4~32h, and then cooled to 600~800℃ for 4~32h at a rate of 1~35℃/h, then air-cooled, and then polished and flat-headed to obtain the electroslag electrode. Generally, the diameter of the resulting electroslag electrode should be matched with the diameter of the matching mold of the vacuum consumable electric arc furnace used in the vacuum consumable remelting step, that is, the diameter of the matching mold and the electrode should maintain an appropriate ratio, that is, filling The ratio is about 0.8 to 0.9.
本申请通过采用上述方案,对真空感应锭直接去应力退火,优点很多,第一,能够及时避免钢锭脱模后因空冷使温度落入时效析出区间形成过大的组织应力;第二,能够以合理的升温速度提升钢锭温度,针对高温合金热导率低的问题,避免钢锭内外产生较大的热应力;第三,在800~1000℃保温一定时间可使钢锭温度充分均匀,释放凝固内应力;第四,通过1~35℃/h的缓冷和600~800℃一定时间保温能够有效避免钢锭再次形成较大的热应力和组织应力。This application adopts the above solution to directly stress-relieve and anneal the vacuum induction ingot. There are many advantages. First, it can prevent the temperature from falling into the aging precipitation zone due to air cooling after the ingot is demolded in time to form excessive structural stress; second, it can be used Reasonable heating rate increases the temperature of the steel ingot, aiming at the problem of low thermal conductivity of the superalloy, avoiding large thermal stress inside and outside the steel ingot; third, keeping the temperature at 800~1000℃ for a certain period of time can make the temperature of the steel ingot fully uniform and release the internal stress of solidification ; Fourth, the slow cooling of 1~35℃/h and the heat preservation of 600~800℃ for a certain time can effectively prevent the steel ingot from forming greater thermal stress and structural stress again.
在优选的实施方案中,进行交换电渣重熔时,所采用的渣系为(CaF 2-CaO-Al 2O 3-TiO 2)四元渣,(CaF 2-CaO-Al 2O 3-TiO 2)四元渣中CaF 2占60~75wt%,CaO占10~25wt%,Al 2O 3占8~13wt%,TiO 2占1~5wt%.在更优选的实施方案中,电渣重熔的稳态熔速控制为5~15kg/min,并且,每次电极交换前,当前一支电极剩余重量500kg~1000kg时,在稳态熔速基础上以0.5~2kg/min的斜率提高熔速至12~25kg/min时,保持稳定至开始交换电渣电极,且交换电极过程保持交换前的冶炼参数,交换时间不超过2min;每次电极交换完成后,当后一支电极熔化100kg~500kg后,以0.5~2kg/min的斜率降低熔速至稳态熔速5~15kg/min,继续重熔,至最后一支电极剩余200~600kg后开始热封顶;交换电渣重熔结束后,冷却2~10h,脱模,得电渣锭。 In a preferred embodiment, when performing exchange electroslag remelting, the slag system used is (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag, (CaF 2 -CaO-Al 2 O 3- TiO 2 ) In the quaternary slag, CaF 2 accounts for 60 to 75 wt%, CaO accounts for 10 to 25 wt%, Al 2 O 3 accounts for 8 to 13 wt%, and TiO 2 accounts for 1 to 5 wt%. In a more preferred embodiment, electroslag The steady-state melting rate of remelting is controlled at 5-15kg/min, and before each electrode exchange, when the remaining weight of the current electrode is 500kg-1000kg, the steady-state melting rate will increase with a slope of 0.5-2kg/min. When the melting rate reaches 12-25kg/min, keep stable until the electroslag electrode is exchanged, and the electrode exchange process keeps the smelting parameters before the exchange, and the exchange time does not exceed 2min; after each electrode exchange is completed, when the next electrode melts 100kg After ~500kg, reduce the melting rate to a steady-state melting rate of 5~15kg/min with a slope of 0.5~2kg/min, continue remelting, and start heat sealing when the last electrode has 200~600kg remaining; exchange electroslag remelting ends After that, it is cooled for 2-10 hours, demoulded, and an electroslag ingot is obtained.
通过采用上述技术方案,针对直径大于1000mm锭型,电渣重熔的稳态 熔速控制为5~15kg/min,后续通过调整交换电极前后的熔速,能够合理增大交换电极时的熔池深度,可以解决交换电极过程时熔炼暂停引起的熔池流动性降低,降低电极瞬间埋入渣池对熔池的扰动,减少夹杂、接注等冶金质量问题。By adopting the above technical solutions, for ingots with diameters greater than 1000mm, the steady-state melting rate of electroslag remelting is controlled to be 5-15kg/min. The subsequent adjustment of the melting rate before and after the electrode exchange can reasonably increase the molten pool when the electrode is exchanged. The depth can solve the decrease of molten pool fluidity caused by the suspension of smelting during the electrode exchange process, reduce the disturbance of the molten pool caused by the instantaneous embedding of the electrode in the slag pool, and reduce the metallurgical quality problems such as inclusions and injection.
在优选的实施方案中,对脱模的电渣锭进行一次退火、二次退火、锻造拔长至预定尺寸以制得一此自耗电极的具体实现方式如下,In a preferred embodiment, the demolded electroslag ingot is subjected to primary annealing, secondary annealing, forging and drawing to a predetermined size to obtain a consumable electrode. The specific implementation method is as follows:
对电渣锭,在脱模后0.5~2h内启动一次退火,具体为,预先加热至300~550℃,保温12~32h实现均温,然后以1~25℃/h的速度升温至600~750℃保温4~32h,而后以5~35℃/h的速度升温至800~1000℃保温4~32h,而后以1~35℃/h的速度冷却至550~750℃保温4~32h,而后空冷;For electroslag ingots, an annealing is started within 0.5-2h after demolding. Specifically, it is preheated to 300-550℃, held for 12-32h to achieve uniform temperature, and then heated at a rate of 1-25℃/h to 600~ Hold at 750°C for 4~32h, then heat up to 800~1000°C at a rate of 5~35℃/h and keep it at 800~1000℃ for 4~32h, then cool to 550~750℃ at a rate of 1~35℃/h and keep it at 4~32h, then Air cooling
对一次退火完成后的电渣锭进行二次退火,具体为,在550~750℃以下保温4~24h,而后以5~35℃/h的速度升温至800~1000℃,而后以1~25℃/h的速度升温至1050~1150℃保温4~32h,而后以1~25℃/h的速度升温至1150~1250℃保温24~72h,而后以1~35℃/h的速度冷却至800~950℃保温4~32h,而后空冷;Perform secondary annealing on the electroslag ingot after the primary annealing. Specifically, keep it at 550~750℃ for 4~24h, then at a rate of 5~35℃/h to 800~1000℃, and then at 1~25℃. Heat up to 1050~1150℃ for 4~32h at a rate of ℃/h, then heat up to 1150~1250℃ for 24~72h at a rate of 1~25℃/h, and then cool to 800 at a rate of 1~35℃/h Keep warm at ~950℃ for 4~32h, then air cooling;
对二次退火后电渣锭,在锻前加热至1100~1180℃,锻前加热时间为4~12h,自由锻采用3000吨以上的快锻机单向拔长,每道次单边压下量控制为5~30mm,终锻温度为850~1000℃;For the electroslag ingot after secondary annealing, it is heated to 1100~1180℃ before forging, and the heating time before forging is 4~12h. The free forging adopts a fast forging machine of more than 3000 tons to draw the length in one direction, and each pass is pressed down on one side. The amount is controlled at 5~30mm, and the final forging temperature is 850~1000℃;
对自由锻拔长之后的钢锭,车光、平头尾,得到一次自耗电极。通常,一次自耗电极的直径应与一次真空自耗重熔所用真空自耗电弧炉的配套结晶器的直径相适配。For the steel ingot after free forging and drawing, the head and tail are flattened, and a consumable electrode is obtained. Generally, the diameter of the primary consumable electrode should be matched with the diameter of the matching mold of the vacuum consumable arc furnace used in the primary vacuum consumable remelting.
采用上述技术方案的原因在于,对获得的高铌高温合金直径为1000mm以上的电渣锭,凝固过程的热应力极大,十分容易炸裂;由于自耗电极和对应的结晶器要求有合理的充填比,该大尺寸的电渣锭无法直接用于一次自耗重熔,需要利用自由锻拔长以减小直径,例如可以是800~900mm;但是由于电渣锭的直径过大,凝固偏析十分严重,存在严重的枝晶元素偏析和枝晶间低熔点相,热塑性极差。The reason for adopting the above technical solution is that the obtained high-niobium superalloy ingots with a diameter of 1000mm or more in the electroslag ingots have great thermal stress during the solidification process and are very easy to burst; due to the reasonable requirements for consumable electrodes and corresponding crystallizers Filling ratio, the large-sized electroslag ingot cannot be directly used for one-time consumable remelting, and free forging is needed to reduce the diameter, for example, it can be 800-900mm; but because the diameter of the electroslag ingot is too large, solidification segregation Very serious, there are severe dendrite element segregation and low melting point phase between dendrites, and the thermoplasticity is extremely poor.
为了解决直径1000mm以上的高铌高温合金电渣锭的热应力问题,于是,本申请在电渣重熔结束后,在所采用的电渣重熔炉内水冷结晶器中通水冷却2~10h,以保证钢锭充分凝固且冷却至时效析出温度以下,脱模后0.5~2h内启动 一次退火。一次退火时,预先加热至300~550℃,避免温度过高产生过大的热应力,而后在300~550℃保温12~32h实现均温,然后以1~25℃/h的速度升温至600~750℃保温4~32h,而后以5~35℃/h的速度升温至800~1000℃保温4~32h,而后以1~35℃/h的速度冷却至550~750℃保温4~32h,而后空冷。通过一次退火,可释放电渣锭凝固过程中由于温度梯度形成的热应力,同时利用过时效处理使强化相粗化避免形成组织应力,进而抑制大尺寸高温合金电渣锭脱模后直接炸裂。In order to solve the problem of thermal stress of high-niobium superalloy electroslag ingots with a diameter of more than 1000mm, the application, after the electroslag remelting is completed, is cooled by water in the water-cooled crystallizer in the adopted electroslag remelting furnace for 2-10 hours. To ensure that the steel ingot is fully solidified and cooled to below the aging precipitation temperature, an annealing is started within 0.5-2h after demolding. In the first annealing, preheat to 300~550℃ to avoid excessive thermal stress caused by excessive temperature, then keep the temperature at 300~550℃ for 12~32h to achieve uniform temperature, and then heat up to 600 at a rate of 1~25℃/h Keep it at ~750℃ for 4~32h, then heat it up to 800~1000℃ at a rate of 5~35℃/h and keep it for 4~32h, and then cool it at a rate of 1~35℃/h to 550~750℃ and keep it for 4~32h, Then air-cooled. Through the one-time annealing, the thermal stress formed by the temperature gradient during the solidification of the electroslag ingot can be released, and at the same time, the over-aging treatment is used to coarsen the strengthening phase to avoid the formation of structural stress, thereby inhibiting the direct explosion of the large-size superalloy electroslag ingot after demolding.
为了提高直径800mm以上的高铌高温合金电渣锭的热塑性,电渣锭应在退火完成后进行二次退火,即高温扩散退火。为了避免热应力过大,升温速度要严格控制,因此,在550~750℃以下温度将电渣锭装炉保温4~24h,而后以5~35℃/h的速度升温至800~1000℃,而后以1~25℃/h的速度升温至1050~1150℃保温4~32h,而后以1~25℃/h的速度升温至1150~1250℃保温24~72h,而后以1~35℃/h的速度冷却至800~950℃保温4~32h,而后空冷。通过多阶段的缓慢升温,可避免钢锭中形成过大的热应力造成炸裂,另外通过高温长时扩散退火,可使合金中的低熔点相回溶、减弱枝晶元素偏析,进而提高钢锭的热塑性,为后续锻造制备自耗电极提供高塑性的钢锭。In order to improve the thermal plasticity of high-niobium superalloy electroslag ingots with a diameter of 800mm or more, the electroslag ingots should be subjected to secondary annealing after annealing, that is, high-temperature diffusion annealing. In order to avoid excessive thermal stress, the heating rate must be strictly controlled. Therefore, the electroslag ingot is kept at a temperature below 550-750°C for 4-24 hours, and then the temperature is raised to 800-1000°C at a rate of 5-35°C/h. Then at a rate of 1~25℃/h to 1050~1150℃ for 4~32h, then at a rate of 1~25℃/h to 1150~1250℃ for 24~72h, then 1~35℃/h It is cooled to 800~950℃ and kept for 4~32h at a high speed, and then air-cooled. Through multi-stage slow heating, it can avoid the formation of excessive thermal stress in the steel ingot to cause explosion. In addition, through high temperature and long-term diffusion annealing, the low melting point phase in the alloy can be re-dissolved, the dendrite element segregation can be weakened, and the thermoplasticity of the steel ingot can be improved. , To provide high-plasticity steel ingots for subsequent forging preparation of consumable electrodes.
在优选的实施方案中,一次真空自耗重熔时,稳态熔速控制为3.5~7.5kg/min;开始熔炼800~2000kg后启动氦气冷却;剩余1500~5000kg后降低电流调整熔速至3.0~7.0kg/min;剩余200~1000kg后启动热封顶,制得一次自耗重熔锭。In a preferred embodiment, during a vacuum consumable remelting, the steady-state melting rate is controlled to be 3.5-7.5kg/min; after 800-2000kg smelting is started, helium cooling is started; after the remaining 1500-5000kg, the current is reduced to adjust the melting rate to 3.0~7.0kg/min; after the remaining 200~1000kg, heat sealing is started to prepare a consumable remelted ingot.
在上述一次真空自耗重熔过程中,由于锭子凝固过程中体积会出现缩小,与结晶器壁出现缝隙,在真空条件下钢锭与结晶器外壁的冷却水无法直接接触实现散热,为此通入氦气导热;熔炼早期钢锭可通过底部与结晶器散热,当熔炼至一定阶段后底部散热受限,为此需要在熔炼一定阶段后通入适量氦气,氦气过多会冲破熔池不利于熔炼稳定性,氦气过少则起不到冷却效果;由于钢锭过大,钢锭凝固越多则热容量越大,传热越困难,为此在熔炼末期需要适当降低熔速,稳定熔池深度,进而降低冶金缺陷的形成几率;根据一次自耗电极剩余重量判断热封顶的时机,能够节省钢锭切除量,提高成材率。In the above-mentioned vacuum consumable remelting process, the volume of the ingot will shrink during solidification, and there will be a gap with the mold wall. Under vacuum conditions, the cooling water of the steel ingot and the outer wall of the mold cannot directly contact the cooling water to achieve heat dissipation. Helium conducts heat; in the early stage of smelting, the steel ingot can dissipate heat through the bottom and the mold. When the smelting reaches a certain stage, the heat dissipation at the bottom is limited. For this reason, it is necessary to pass in a proper amount of helium after a certain stage of smelting. Melting stability, too little helium gas will not have the cooling effect; because the steel ingot is too large, the more the ingot solidifies, the greater the heat capacity and the more difficult the heat transfer. Therefore, at the end of smelting, it is necessary to appropriately reduce the melting rate and stabilize the depth of the molten pool. In turn, the probability of formation of metallurgical defects is reduced; the timing of heat sealing is judged according to the remaining weight of a consumable electrode, which can save the amount of steel ingot removal and increase the yield rate.
在优选的实施方案中,在进行二次真空自耗重熔之前,首先对一次自耗 重熔锭车光、平头尾,得到直径直径与二次真空自耗重熔所用结晶器直径相适配的二次自耗电极;进行二次真空自耗重熔时,稳态熔速控制为4.0~8.5kg/min;开始熔炼1000~3000kg后通入氦气冷却;剩余2000~5500kg后降低电流调整熔速至3.0~7.5kg/min;剩余250~1500kg后启动热封顶;In a preferred embodiment, before the secondary vacuum consumable remelting, the primary consumable remelting ingot is first polished and flattened to obtain a diameter that matches the diameter of the crystallizer used in the secondary vacuum consumable remelting The secondary consumable electrode; when performing secondary vacuum consumable remelting, the steady-state melting rate is controlled to be 4.0~8.5kg/min; after smelting 1000~3000kg, it is cooled by helium gas; the current is reduced after the remaining 2000~5500kg Adjust the melting rate to 3.0~7.5kg/min; start heat sealing after the remaining 250~1500kg;
在优选的实施方案中,二次自耗重熔完成后,真空冷却1~8h,而后在2h内启动去应力退火;退火时,预先加热至300~750℃,保温4~32h实现均温,然后以5~50℃/h的速度升温至800~1000℃,保温4~32h,而后以1~35℃/h的速度冷却至550~750℃保温4~32h,而后空冷。In a preferred embodiment, after the secondary consumable remelting is completed, vacuum cooling is performed for 1 to 8 hours, and then stress relief annealing is started within 2 hours; during annealing, it is preheated to 300 to 750°C and kept for 4 to 32 hours to achieve uniform temperature. Then the temperature is raised to 800-1000°C at a rate of 5-50°C/h, kept for 4 to 32 hours, and then cooled to 550-750°C at a rate of 1 to 35°C/h for 4 to 32 hours, and then air-cooled.
在一次真空自耗重熔过程中,由于一次自耗电极是利用多支真空感应锭交换电渣重熔制备的电渣锭锻制而成的,电极交换接头处存在着冶金质量的波动,即使通过高温扩散和锻造也无法完全消除。由于自耗重熔过程对电极质量十分敏感,在重熔至电极交换接头处时易出现熔速波动、电极掉块等异常问题,易形成黑斑和白斑等冶金缺陷,且无法通过后续的高温扩散退火、锻造或热处理工序消除,严重时会直接造成所制备的棒材或锻件报废。为此,本申请将一次自耗重熔锭车光、平头尾以制备二次自耗电极,再进行二次自耗重熔。由于二次自耗重熔后的钢锭直径超过800mm,会存在很大的热应力,故在二次自耗重熔完成后,要真空冷却,而后破空在2h内启动去应力退火,避免钢锭脱模后炸裂,退火时应预先加热至300~750℃保温4~32h实现均温,然后以5~50℃/h的速度升温至800~1000℃保温4~32h,而后以1~35℃/h的速度冷却至550~750℃保温4~32h,而后空冷,后续采用这种方式,可释放一次自耗重熔锭凝固过程中由于温度梯度形成的热应力,同时利用过时效处理,使强化相粗化,避免形成组织应力,进而抑制大尺寸高温合金电渣锭脱模后直接炸裂。In a vacuum consumable remelting process, since the primary consumable electrode is forged by using multiple vacuum induction ingots to exchange electroslag ingots prepared by electroslag remelting, there are fluctuations in metallurgical quality at the electrode exchange joints. Even through high temperature diffusion and forging, it cannot be completely eliminated. Since the consumable remelting process is very sensitive to the quality of the electrode, it is prone to abnormal problems such as melting rate fluctuations and electrode blockage when remelting to the electrode exchange joint. It is easy to form metallurgical defects such as black and white spots, and cannot pass the subsequent high temperature. Diffusion annealing, forging or heat treatment processes are eliminated, which will directly cause the prepared bars or forgings to be scrapped in severe cases. For this reason, this application will turn the primary consumable remelting ingots, flat head and tail to prepare secondary consumable electrodes, and then perform secondary consumable remelting. Since the diameter of the steel ingot after the secondary consumable remelting exceeds 800mm, there will be great thermal stress, so after the secondary consumable remelting is completed, vacuum cooling is required, and then the stress relief annealing is started within 2h to avoid the steel ingot. After demolding, it bursts. During annealing, it should be preheated to 300~750℃ and kept for 4~32h to achieve uniform temperature, then at a rate of 5~50℃/h to 800~1000℃ and kept for 4~32h, and then at 1~35℃ Cooling to 550~750℃ for 4~32h at a rate of /h, and then air cooling. The subsequent use of this method can release the thermal stress formed by the temperature gradient during the solidification of the consumable remelted ingot. At the same time, the over-aging treatment is used to make The strengthening phase is coarsened to avoid the formation of structural stress, thereby inhibiting the direct explosion of large-size superalloy electroslag ingots after demolding.
本发明具有以下优点:The invention has the following advantages:
1、本发明提供的用于制备大尺寸高铌高温706合金的方法,通过合理控制钢液中Al的添加量,并在交换电渣重熔过程中采用特定的四元渣系,可使得过程中无Al、Ti元素无明显烧损。1. The method for preparing large-size, high-niobium, high-temperature 706 alloy provided by the present invention, by reasonably controlling the amount of Al added in the molten steel, and adopting a specific quaternary slag system in the exchange electroslag remelting process, can make the process There is no Al and Ti elements and no obvious burning loss.
2、本发明能够突破感应炉和气氛保护电渣炉的吨位限制,采用常规吨位(如12吨)真空感应炉制备2支电极,再利用电渣炉交换电极将2支感应锭熔炼为1支电渣锭,再用于制造至少15吨级的真空自耗锭;2. The present invention can break through the tonnage limit of induction furnace and atmosphere protection electroslag furnace, adopting conventional tonnage (such as 12 tons) vacuum induction furnace to prepare 2 electrodes, and then using electroslag furnace to exchange electrodes to smelt 2 induction ingots into 1 Electroslag ingots, which are then used to manufacture vacuum consumable ingots of at least 15 tons;
3、能够利用电极支臂吨位受限制的电渣炉,采用交换电渣重熔的方法制备20吨级的高温合金电渣锭;3. The electroslag furnace with limited tonnage of the electrode arm can be used to prepare 20-ton high-temperature alloy electroslag ingots by the method of exchange electroslag remelting;
4、通过交换电渣重熔制备的电渣锭经高温扩散退火获得一定热塑性,再利用自由锻造开坯拔长制备合适直径的自耗电极,可以显著改善一次自耗重熔过程的熔炼稳定性;4. Electroslag ingots prepared by exchange electroslag remelting are subjected to high temperature diffusion annealing to obtain a certain degree of thermoplasticity, and then free forging is used to open the billet to prepare a consumable electrode with a suitable diameter, which can significantly improve the melting stability of a consumable remelting process. Sex
5、采用一次自耗重熔钢锭制备的二次自耗电极用于二次自耗重熔,必要时,进一步进行多次自耗重熔,能够有效解决交换电渣重熔过程中电渣锭交换电极接头处的夹杂等冶金缺陷问题,以制备直径800mm以上、锭重超过15吨的无冶金缺陷的高铌高温合金自耗锭。5. The secondary consumable electrode prepared by the primary consumable remelting steel ingot is used for the secondary consumable remelting. If necessary, further consumable remelting is performed multiple times, which can effectively solve the electroslag exchange during the electroslag remelting process. Metallurgical defects such as inclusions at the ingot exchange electrode joints are used to prepare high-niobium superalloy consumable ingots with a diameter of 800mm or more and an ingot weight of more than 15 tons without metallurgical defects.
具体实施方式detailed description
以下结合实施例对本发明作进一步详细说明。Hereinafter, the present invention will be further described in detail with reference to the embodiments.
实施例1:Example 1:
本实施例用于说明制备706合金(直径1050mm自耗锭)的方法。This embodiment is used to illustrate the method of preparing 706 alloy (a consumable ingot with a diameter of 1050 mm).
目标706合金成分(按质量百分比):Target 706 alloy composition (by mass percentage):
C 0.018%,Cr 15.8%,Ni 41.5%,Nb3.01%,Ti1.72%,Al 0.25%,Si0.02%,Mn0.01%,P0.006%,S0.0006%,Co0.02%,Mo0.01%,B0.004%,Cu0.02%,Ca0.004%,N0.005%,O0.002%,Fe余量。C 0.018%, Cr 15.8%, Ni 41.5%, Nb3.01%, Ti1.72%, Al 0.25%, Si0.02%, Mn0.01%, P0.006%, S0.0006%, Co0.02% , Mo0.01%, B0.004%, Cu0.02%, Ca0.004%, N0.005%, O0.002%, Fe balance.
具体制备方法如下:The specific preparation method is as follows:
真空感应熔炼:根据设计的合金成分要求,按单位重量的合金所需元素称取50%返回料,剩余采用全新金属原材料。采用12吨真空感应炉,熔化温度上限为1550℃,熔清后检测钢液成分,通过补加新金属,控制钢液中Ni含量约42.0wt%,Nb含量约3.02wt%,Ti含量约1.80wt%,Al含量约0.30wt%;根据补加金属料的数量,采用电磁搅拌下精炼15-30min,精炼温度为1350℃,出钢温度为1400℃。浇钢完成后,炉冷4小时后脱模,制得2支直径820mm的12吨真空电极锭,然后直接进行退火处理。退火炉预先加热至600℃,而后以5℃/h的速度升温至800℃保温24h,而后以1℃/h的速度冷却至600℃保温10h,而后空冷。Vacuum induction smelting: According to the designed alloy composition requirements, 50% of the return material is weighed according to the required elements of the alloy per unit weight, and the rest is made of new metal raw materials. Using a 12-ton vacuum induction furnace, the upper limit of the melting temperature is 1550℃. After melting, the composition of the molten steel is detected. By adding new metal, the content of Ni in the molten steel is controlled to be about 42.0wt%, the content of Nb is about 3.02wt%, and the content of Ti is about 1.80 wt%, Al content is about 0.30wt%; according to the amount of added metal material, refining is performed under electromagnetic stirring for 15-30 minutes, the refining temperature is 1350°C, and the tapping temperature is 1400°C. After pouring the steel, the furnace is cooled for 4 hours and then demolded to obtain two 12-ton vacuum electrode ingots with a diameter of 820 mm, which are then directly annealed. The annealing furnace is preheated to 600°C, and then heated at a rate of 5°C/h to 800°C for 24 hours, and then cooled at a rate of 1°C/h to 600°C for 10 hours, and then air-cooled.
将退火后的真空感应锭车/磨光、平头尾,用于制备电渣电极。The annealed vacuum induction ingot car/polishing, flat head and tail are used to prepare the electroslag electrode.
电渣重熔:结晶器选用直径1100mm,渣系选用(CaF 2-CaO-Al 2O 3-TiO 2)四元渣,具体组成为:CaF 260%,CaO10%,Al 2O 313%,TiO 210%。稳态熔速为 15kg/min,熔炼过程中通入0.2bar压力的Ar气保护,避免熔炼过程中钢液与空气中的氧气和氮气接触。电极交换前,在剩余重量800kg时,调整输入功率和电压提高熔速,在稳态熔速基础上以1.05kg/min的斜率提高熔速,至25kg/min时保持稳定至开始交换电渣电极。交换电极过程保持交换前的冶炼参数,交换时间不能超过2min。交换电极完成后,第二支电极熔化100kg后,通过调整输入功率和电压提高熔速,以0.50kg/min的斜率降低至10kg/min,至第二支电极剩余200kg后开始热封顶。 Electroslag remelting: The diameter of the crystallizer is 1100mm, and the slag system is (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag. The specific composition is: CaF 2 60%, CaO 10%, Al 2 O 3 13% , TiO 2 10%. The steady-state melting rate is 15kg/min, and Ar gas protection at a pressure of 0.2bar is introduced during the melting process to prevent the molten steel from contacting oxygen and nitrogen in the air during the melting process. Before the electrode exchange, when the remaining weight is 800kg, adjust the input power and voltage to increase the melting rate. On the basis of the steady-state melting rate, increase the melting rate with a slope of 1.05kg/min. When it reaches 25kg/min, it will remain stable until the electroslag electrode is exchanged. . The electrode exchange process maintains the smelting parameters before the exchange, and the exchange time cannot exceed 2 min. After the electrode exchange is completed, after the second electrode melts 100kg, the melting rate is increased by adjusting the input power and voltage, and the melting rate is reduced to 10kg/min at a slope of 0.50kg/min. After the second electrode remains 200kg, the heat sealing starts.
电渣重熔结束后,在炉内水冷结晶器中通水冷却4h,脱模后0.5h内转移至退火炉内去应力退火。退火炉应预先加热至300℃,在300℃保温12h,然后以5℃/h的速度升温至600℃保温4h,而后以10℃/h的速度升温至800℃保温5h,而后以5℃/h的速度冷却至600℃保温12h,而后空冷。After the electroslag remelting is completed, the water-cooled crystallizer in the furnace is cooled by water for 4 hours, and within 0.5 hours after demolding, it is transferred to the annealing furnace for stress relief annealing. The annealing furnace should be pre-heated to 300°C, kept at 300°C for 12h, then at a rate of 5°C/h to 600°C for 4h, then at a rate of 10°C/h to 800°C for 5h, and then at 5°C/h Cool down to 600°C for 12 hours at a rate of h, then cool in air.
电渣锭高温扩散退火:在550℃以下温度装炉保温4h,而后以10℃/h的速度升温至800℃,而后以5℃/h的速度升温至1050℃保温4h,而后以5℃/h的速度升温至1150℃保温24h,而后以5℃/h的速度冷却至800℃保温32h,而后空冷。High temperature diffusion annealing of electroslag ingots: install the furnace at a temperature below 550°C for 4 hours, then heat up to 800°C at a rate of 10°C/h, then heat up to 1050°C at a rate of 5°C/h, hold for 4 hours, and then heat at 5°C/h The temperature was raised to 1150°C for 24 hours at a rate of h, and then cooled to 800°C for 32 hours at a rate of 5°C/h, and then air-cooled.
电极锻制:直径1100mm电渣锭的锻前加热温度选用1100℃,锻前加热时间为4h。自由锻采用3500吨快锻机单向拔长,每道次单边压下量控制为25mm,终锻温度为850℃,最终经锻制、车光、平头尾制备为直径820mm一次自耗电极,用于一次真空自耗重熔。Electrode forging: The heating temperature before forging of the electroslag ingot with a diameter of 1100mm is 1100℃, and the heating time before forging is 4h. The free forging adopts a 3500 ton fast forging machine to draw length in one direction, and the unilateral reduction of each pass is controlled to 25mm, the final forging temperature is 850℃, and the final forging, turning, and flat head and tail are prepared to a diameter of 820mm. Extremely, used for a vacuum consumable remelting.
一次真空自耗重熔:结晶器选用直径920mm,自耗重熔通过熔速进行控制,稳态熔速控制为3.5kg/min;开始熔炼800kg后启动氦气冷却;剩余1500kg后降低电流调整熔速至3.0kg/min;剩余200kg后启动热封顶,热封顶通过电流控制。将一次自耗重熔锭车光、平头尾加工至直径900mm,用于二次真空自耗重熔。One-time vacuum consumable remelting: The diameter of the crystallizer is 920mm, the consumable remelting is controlled by the melting rate, and the steady-state melting rate is controlled to 3.5kg/min; the helium cooling is started after 800kg of smelting; after the remaining 1500kg, the current is reduced to adjust the melting The speed reaches 3.0kg/min; after the remaining 200kg, the heat sealing is started, and the heat sealing is controlled by the current. The primary consumable remelting ingot is machined and flat-headed to a diameter of 900mm, which is used for secondary vacuum consumable remelting.
二次真空自耗重熔:结晶器选用1050mm,熔通过熔速进行控制,稳态熔速控制为4.0kg/min;开始熔炼1000kg后启动氦气冷却;剩余2000kg后降低电流调整熔速至3.0kg/min;剩余250kg后启动热封顶,热封顶通过电流控制。二次真空自耗重熔完成后,真空冷却3h,而后破空在2h内转移至退火炉内去应力退火,避免钢锭脱模后炸裂。退火炉应预先加热至300℃保温4h实现均温,然 后以5℃/h的速度升温至800℃保温5h,而后以5℃/h的速度冷却至550℃保温5h,而后空冷。Secondary vacuum self-consumption remelting: 1050mm is used for the crystallizer, the melting is controlled by the melting rate, and the steady-state melting rate is controlled to 4.0kg/min; the helium cooling is started after the smelting of 1000kg; after the remaining 2000kg, the current is reduced to adjust the melting rate to 3.0 kg/min; after the remaining 250kg, the heat sealing is started, and the heat sealing is controlled by the current. After the secondary vacuum consumable remelting is completed, it is vacuum cooled for 3 hours, and then the void is transferred to the annealing furnace for stress relief annealing within 2 hours to avoid the steel ingot from bursting after demolding. The annealing furnace should be preheated to 300°C for 4 hours to achieve uniform temperature, then heated at a rate of 5°C/h to 800°C for 5 hours, and then cooled at a rate of 5°C/h to 550°C for 5 hours, and then air-cooled.
试验结果:试制的706合金1050mm自耗锭,重量为15.5吨,未出现热裂,且无黑斑、白斑等冶金缺陷。对钢锭的头尾进行成分测试,测试结果表明,头尾Al、Ti元素无明显烧损,Al元素为头部0.27%、尾部0.24%,Ti元素为头部1.68%、尾部1.78%。将直径1050mm的二次自耗重熔锭高温均匀化扩散退火处理后,车光后安排锻造,制备锻造棒材。棒材经无损探伤检验,发现电渣重熔接头处无异常信号,表明通过二次真空自耗重熔可以有效解决706合金电渣接头处的冶金质量问题。Test result: The trial-produced 1050mm consumable ingot of 706 alloy weighs 15.5 tons, and there is no hot cracking, and no metallurgical defects such as black spots and white spots. The composition test on the head and tail of the steel ingot showed that the Al and Ti elements at the head and tail have no obvious burning loss. The Al element is 0.27% at the head and 0.24% at the tail. The Ti element is 1.68% at the head and 1.78% at the tail. After the secondary consumable remelted ingot with a diameter of 1050mm is homogenized at high temperature and diffused and annealed, after finishing, forging is arranged to prepare forged bars. After non-destructive inspection of the bar, it was found that there was no abnormal signal at the electroslag remelting joint, indicating that the secondary vacuum consumable remelting can effectively solve the metallurgical quality problem at the 706 alloy electroslag joint.
实施例2Example 2
本实施例用于说明制备706合金(直径1050mm自耗锭)的方法。This embodiment is used to illustrate the method of preparing 706 alloy (a consumable ingot with a diameter of 1050 mm).
目标706合金成分(按质量百分比):Target 706 alloy composition (by mass percentage):
C 0.011%,Cr 16.2%,Ni 42.2%,Nb2.88%,Ti1.60%,Al 0.18%,Si 0.02%,Mn 0.02%,P 0.008%,S 0.0004%,Co 0.01%,Mo 0.02%,B 0.003%,Cu 0.05%,Ca 0.001%,N 0.0045%,O 0.0025%,Fe余量。C 0.011%, Cr 16.2%, Ni 42.2%, Nb 2.88%, Ti1.60%, Al 0.18%, Si 0.02%, Mn 0.02%, P 0.008%, S 0.0004%, Co 0.01%, Mo 0.02%, B 0.003%, Cu 0.05%, Ca 0.001%, N 0.0045%, O 0.0025%, Fe balance.
具体制备方法如下:The specific preparation method is as follows:
真空感应熔炼:根据设计的合金成分要求,按单位重量的合金所需元素称取50%返回料,剩余采用全新金属原材料。采用12吨真空感应炉,熔化温度上限为1550℃,熔清后检测钢液成分,通过补加新金属,控制钢液中Ni含量约42.5wt%,Nb含量约2.92wt%,Ti含量约1.65wt%,Al含量约0.22wt%,采用电磁搅拌下精炼40min,精炼温度为1480℃,出钢温度为1500℃。分两次浇钢,完成后,炉冷4小时后脱模,制得2支直径820mm的12吨自耗锭,然后直接进行退火处理。退火炉预先加热至650℃,而后以25℃/h的速度升温至900℃保温24h,而后以15℃/h的速度冷却至700℃保温10h,而后空冷。Vacuum induction smelting: According to the designed alloy composition requirements, 50% of the return material is weighed according to the required elements of the alloy per unit weight, and the rest is made of new metal raw materials. A 12-ton vacuum induction furnace is used. The upper limit of the melting temperature is 1550℃. After melting, the composition of the molten steel is detected. By adding new metal, the content of Ni in the molten steel is controlled to be about 42.5% by weight, the content of Nb is about 2.92% by weight, and the content of Ti is about 1.65. wt%, Al content is about 0.22wt%, refining under electromagnetic stirring for 40 minutes, the refining temperature is 1480°C, and the tapping temperature is 1500°C. The steel was poured in two times. After completion, the furnace was cooled for 4 hours and then demolded to obtain two 12-ton consumable ingots with a diameter of 820mm, which were then directly annealed. The annealing furnace is preheated to 650°C, and then heated to 900°C at a rate of 25°C/h for 24 hours, and then cooled to 700°C at a rate of 15°C/h for 10 hours, and then air-cooled.
将退火后的真空感应锭车光、平头尾,用于制备电渣电极。The annealed vacuum induction ingots are turned and flattened to prepare electroslag electrodes.
电渣重熔:结晶器选用直径1100mm,渣系选用(CaF 2-CaO-Al 2O 3-TiO 2)四元渣,具体组成为:CaF 264%,CaO 15%,Al 2O 3 10%,TiO 2 6%。稳态熔速为10kg/min,熔炼过程中通入0.2bar压力的Ar气保护,避免熔炼过程中钢液与空气中的氧气和氮气接触。电极交换前,在剩余重量500kg时,调整输入功率和电 压提高熔速,在稳态熔速基础上以0.75kg/min的斜率提高熔速,至12kg/min时保持稳定至开始交换电渣电极。交换电极过程保持交换前的冶炼参数,交换时间不能超过2min。交换电极完成后,第二支电极熔化300kg后,通过调整输入功率和电压提高熔速,以1.5kg/min的斜率降低至6kg/min,至第二支电极剩余500kg后开始热封顶。 Electroslag remelting: The diameter of the crystallizer is 1100mm, and the slag system is (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag. The specific composition is: CaF 2 64%, CaO 15%, Al 2 O 3 10 %, TiO 2 6%. The steady-state melting rate is 10kg/min, and Ar gas protection at 0.2bar pressure is introduced during the smelting process to prevent the molten steel from contacting oxygen and nitrogen in the air during the smelting process. Before electrode exchange, when the remaining weight is 500kg, adjust the input power and voltage to increase the melting rate, and increase the melting rate with a slope of 0.75kg/min on the basis of the steady-state melting rate. When it reaches 12kg/min, it remains stable until the electroslag electrode is exchanged. . The electrode exchange process maintains the smelting parameters before the exchange, and the exchange time cannot exceed 2 min. After the electrode exchange is completed, after the second electrode melts 300kg, the melting rate is increased by adjusting the input power and voltage, and the melting rate is reduced to 6kg/min at a slope of 1.5kg/min. After the second electrode is left with 500kg, the heat sealing starts.
电渣重熔结束后,在炉内水冷结晶器中通水冷却4h,脱模后2h内转移至退火炉内去应力退火。退火炉应预先加热至350℃,在350℃保温24h,然后以20℃/h的速度升温至650℃保温30h,而后以25℃/h的速度升温至900℃保温72h,而后以30℃/h的速度冷却至550℃保温32h,而后空冷。After the electroslag remelting is completed, the water-cooled crystallizer in the furnace is cooled by water for 4 hours, and after demolding, it is transferred to the annealing furnace for stress relief annealing within 2 hours. The annealing furnace should be preheated to 350°C, kept at 350°C for 24h, then at a rate of 20°C/h to 650°C for 30h, then at a rate of 25°C/h to 900°C for 72h, and then at 30°C/h Cool down to 550°C for 32 hours at a rate of h, then cool in air.
电渣锭高温扩散退火:在550℃以下温度装炉保温4h,而后以15℃/h的速度升温至1000℃,而后以25℃/h的速度升温至1150℃保温12h,而后以25℃/h的速度升温至1250℃保温72h,而后以35℃/h的速度冷却至950℃保温8h,而后空冷。High temperature diffusion annealing of electroslag ingots: install the furnace at a temperature below 550°C for 4 hours, then heat up to 1000°C at a rate of 15°C/h, then heat up to 1150°C at a rate of 25°C/h, hold for 12 hours, and then hold at 25°C/h The temperature was raised to 1250°C for 72 hours at a rate of h, and then cooled to 950°C at a rate of 35°C/h for 8 hours, and then air-cooled.
电极锻制:直径1100mm电渣锭的锻前加热温度选用1180℃,锻前加热时间为12h。自由锻采用3500吨快锻机单向拔长,每道次单边压下量控制为30mm,终锻温度为1000℃,最终经锻制、车光、平头尾制备为直径820mm一次自耗电极,用于一次真空自耗重熔。Electrode forging: The heating temperature before forging of the electroslag ingot with a diameter of 1100mm is 1180℃, and the heating time before forging is 12h. Free forging adopts 3500 ton fast forging machine to draw length in one direction, the single side reduction of each pass is controlled to 30mm, the final forging temperature is 1000℃, and the final forging, turning, and flat head and tail are prepared to a diameter of 820mm. Extremely, used for a vacuum consumable remelting.
一次真空自耗重熔:结晶器选用直径920mm,自耗重熔通过熔速进行控制,稳态熔速控制为7.5kg/min;开始熔炼1800kg后启动氦气冷却;剩余5000kg后降低电流调整熔速至7.0kg/min;剩余1500kg后启动热封顶,热封顶通过电流控制。将一次自耗重熔锭车光、平头尾加工至直径900mm,用于二次真空自耗重熔。One-time vacuum consumable remelting: The diameter of the crystallizer is 920mm, and the consumable remelting is controlled by the melting rate. The steady-state melting rate is controlled to 7.5kg/min; the helium cooling is started after 1800kg of smelting; after the remaining 5000kg, the current is reduced and the melting is adjusted. The speed reaches 7.0kg/min; after the remaining 1500kg, the heat sealing is started, and the heat sealing is controlled by the current. The primary consumable remelting ingot is machined and flat-headed to a diameter of 900mm, which is used for secondary vacuum consumable remelting.
二次真空自耗重熔:结晶器选用1050mm,熔通过熔速进行控制,稳态熔速控制为8.5kg/min;开始熔炼3000kg后启动氦气冷却;剩余5500kg后降低电流调整熔速至7.5kg/min;剩余1500kg后启动热封顶,热封顶通过电流控制。二次真空自耗重熔完成后,真空冷却8h,而后破空在2h内转移至退火炉内去应力退火,避免钢锭脱模后炸裂。退火炉应预先加热至750℃保温32h实现均温,然后以35℃/h的速度升温至1000℃保温32h,而后以25℃/h的速度冷却至750℃保温32h,而后空冷,即得目标铸锭。Secondary vacuum self-consumption remelting: 1050mm is selected for the crystallizer, the melting is controlled by the melting rate, and the steady-state melting rate is controlled at 8.5kg/min; after 3000kg of smelting starts, helium cooling is started; after the remaining 5500kg, the current is reduced to adjust the melting rate to 7.5 kg/min; after the remaining 1500kg, the heat sealing is started, and the heat sealing is controlled by the current. After the secondary vacuum consumable remelting is completed, it is vacuum cooled for 8 hours, and then the void is transferred to the annealing furnace for stress relief annealing within 2 hours to prevent the steel ingot from bursting after demoulding. The annealing furnace should be preheated to 750°C for 32 hours to achieve uniform temperature, and then heated at a rate of 35°C/h to 1000°C for 32 hours, and then cooled at a rate of 25°C/h to 750°C for 32 hours, and then air-cooled to achieve the target Ingot casting.
试验结果:试制的706合金1050mm自耗锭,重量为15.5吨,未出现热裂,且无黑斑、白斑等冶金缺陷。对钢锭的头尾进行成分测试,测试结果表明,头尾Al、Ti元素无明显烧损,Al元素为头部为0.24%、尾部为0.19%,Ti元素为头部为1.68%、尾部为1.50%。将直径1050mm的三次自耗重熔锭高温均匀化扩散退火处理后,车光后安排锻造,制备锻造棒材。棒材经无损探伤检验,发现电渣重熔接头处无异常信号,表明通过三次真空自耗重熔可以有效解决706合金电渣接头处的冶金质量问题。Test result: The trial-produced 1050mm consumable ingot of 706 alloy weighs 15.5 tons, and there is no hot cracking, and no metallurgical defects such as black spots and white spots. The composition test on the head and tail of the steel ingots shows that there is no obvious burning loss of Al and Ti elements at the head and tail. Al element is 0.24% for the head and 0.19% for the tail, Ti element is 1.68% for the head and 1.50 for the tail. %. After the three-time consumable remelted ingot with a diameter of 1050mm is homogenized at high temperature and diffused and annealed, it is arranged for forging after polishing to prepare forged bars. After non-destructive testing of the bar, it was found that there was no abnormal signal at the electroslag remelting joint, indicating that the three-time vacuum consumable remelting can effectively solve the metallurgical quality problem at the 706 alloy electroslag joint.
实施例3Example 3
本实施例用于说明制备706合金(直径1050mm自耗锭)的方法。This embodiment is used to illustrate the method of preparing 706 alloy (a consumable ingot with a diameter of 1050 mm).
目标706合金成分(按质量百分比):Target 706 alloy composition (by mass percentage):
C 0.015%,Cr 16.6%,Ni 40.0%,Nb3.18%,Ti1.51%,Al 0.10%,Si 0.01%,Mn 0.15%,P 0.007%,S 0.0005%,Co 0.03%,Mo 0.03%,B 0.005%,Cu0 0.04%,Ca 0.002%,N 0.004%,O 0.003%,Fe余量。C 0.015%, Cr 16.6%, Ni 40.0%, Nb 3.18%, Ti 1.51%, Al 0.10%, Si 0.01%, Mn 0.15%, P 0.007%, S 0.0005%, Co 0.03%, Mo 0.03%, B 0.005%, Cu0 0.04%, Ca 0.002%, N 0.004%, O 0.003%, Fe balance.
具体制备方法如下:The specific preparation method is as follows:
真空感应熔炼:根据设计的合金成分要求,按单位重量的合金所需元素称取60%返回料,剩余采用全新金属原材料。采用12吨真空感应炉,熔化温度上限为1350℃,熔清后检测钢液成分,通过补加新金属,控制钢液中Ni含量约40.5wt%,Nb含量约3.2wt%,Ti含量约1.57wt%,Al含量约0.15wt%,采用电磁搅拌下精炼100min,精炼温度为1400℃,出钢温度为1450℃。分两次浇钢,完成后,炉冷4小时后脱模,制得2支直径820mm的12吨自耗锭,然后直接进行退火处理。退火炉预先加热至750℃,而后以40℃/h的速度升温至1000℃保温24h,而后以30℃/h的速度冷却至800℃保温30h,而后空冷。Vacuum induction smelting: According to the designed alloy composition requirements, 60% of the return material is weighed according to the required elements of the alloy per unit weight, and the rest is made of new metal raw materials. A 12-ton vacuum induction furnace is used. The upper limit of the melting temperature is 1350℃. After melting, the composition of the molten steel is detected. By adding new metal, the content of Ni in the molten steel is controlled to be about 40.5wt%, the content of Nb is about 3.2wt%, and the content of Ti is about 1.57 wt%, Al content is about 0.15wt%, refining under electromagnetic stirring for 100 minutes, the refining temperature is 1400°C, and the tapping temperature is 1450°C. The steel was poured in two times. After completion, the furnace was cooled for 4 hours and then demolded to obtain two 12-ton consumable ingots with a diameter of 820mm, which were then directly annealed. The annealing furnace is pre-heated to 750°C, and then heated to 1000°C at a rate of 40°C/h for 24 hours, then cooled to 800°C at a rate of 30°C/h for 30 hours, and then air-cooled.
将退火后的真空感应锭车光、平头尾,用于制备电渣电极。The annealed vacuum induction ingots are turned and flattened to prepare electroslag electrodes.
电渣重熔:结晶器选用直径1100mm,渣系选用(CaF2-CaO-Al2O3-TiO2)四元渣,具体组成为:CaF264%,CaO 15%,Al2O3 8%,TiO2 1%。稳态熔速为5kg/min,熔炼过程中通入0.2bar压力的Ar气保护,避免熔炼过程中钢液与空气中的氧气和氮气接触。Electroslag remelting: The diameter of the crystallizer is 1100mm, and the slag system is (CaF2-CaO-Al2O3-TiO2) quaternary slag. The specific composition is: CaF264%, CaO 15%, Al2O3 8%, TiO2 1%. The steady-state melting rate is 5kg/min, and Ar gas protection at 0.2bar pressure is introduced during the smelting process to prevent the molten steel from contacting oxygen and nitrogen in the air during the smelting process.
电极交换前,在剩余重量600kg时,调整输入功率和电压提高熔速,在稳态熔速基础上以2kg/min的斜率提高熔速,至20kg/min时保持稳定至开始交 换电渣电极。交换电极过程保持交换前的冶炼参数,交换时间不能超过2min。交换电极完成后,第二支电极熔化500kg后,通过调整输入功率和电压提高熔速,以2kg/min的斜率降低至15kg/min,至第二支电极剩余500kg后开始热封顶。Before the electrode exchange, when the remaining weight is 600kg, adjust the input power and voltage to increase the melting rate. On the basis of the steady-state melting rate, increase the melting rate with a slope of 2kg/min. When it reaches 20kg/min, it will remain stable until the electroslag electrode is exchanged. The electrode exchange process maintains the smelting parameters before the exchange, and the exchange time cannot exceed 2 min. After the electrode exchange is completed, after the second electrode melts 500kg, the melting rate is increased by adjusting the input power and voltage, and the melting rate is reduced to 15kg/min at a slope of 2kg/min. When the second electrode remains 500kg, the heat sealing starts.
电渣重熔结束后,在炉内水冷结晶器中通水冷却4h,脱模后1h内转移至退火炉内去应力退火。退火炉应预先加热至550℃,在400℃保温24h,然后以15℃/h的速度升温至750℃保温24h,而后以18℃/h的速度升温至1000℃保温36h,而后以15℃/h的速度冷却至750℃保温12h,而后空冷。After the electroslag remelting is completed, the water-cooled crystallizer in the furnace is cooled by water for 4 hours, and the mold is transferred to the annealing furnace for stress relief annealing within 1 hour. The annealing furnace should be preheated to 550°C, kept at 400°C for 24h, then at a rate of 15°C/h to 750°C for 24h, then at a rate of 18°C/h to 1000°C for 36h, and then at 15°C/h It is cooled to 750°C for 12 hours at a rate of h, and then air-cooled.
电渣锭高温扩散退火:在550℃以下温度装炉保温4h,而后以10℃/h的速度升温至950℃,而后以15℃/h的速度升温至1100℃保温12h,而后以20℃/h的速度升温至1200℃保温48h,而后以15℃/h的速度冷却至850℃保温24h,而后空冷。High temperature diffusion annealing of electroslag ingots: install the furnace at a temperature below 550°C for 4 hours, then heat up to 950°C at a rate of 10°C/h, then heat up to 1100°C at a rate of 15°C/h, hold for 12 hours, and then at 20°C/h The temperature was raised to 1200°C for 48 hours at a rate of h, and then cooled to 850°C at a rate of 15°C/h for 24 hours, and then air-cooled.
电极锻制:直径1100mm电渣锭的锻前加热温度选用1150℃,锻前加热时间为8h。自由锻采用3500吨快锻机单向拔长,每道次单边压下量控制为5mm,终锻温度为900℃,最终经锻制、车光、平头尾制备为直径820mm一次自耗电极,用于一次真空自耗重熔。Electrode forging: The heating temperature before forging of the electroslag ingot with a diameter of 1100mm is 1150℃, and the heating time before forging is 8h. The free forging adopts a 3500 tons fast forging machine to draw length in one direction, and the unilateral reduction of each pass is controlled to 5mm, and the final forging temperature is 900℃. The final forging, turning, and flat head and tail are prepared to a diameter of 820mm. Extremely, used for a vacuum consumable remelting.
一次真空自耗重熔:结晶器选用直径920mm,自耗重熔通过熔速进行控制,稳态熔速控制为5.0kg/min;开始熔炼1500kg后启动氦气冷却;剩余2000kg后降低电流调整熔速至6.0kg/min;剩余250kg后启动热封顶,热封顶通过电流控制。将一次自耗重熔锭车光、平头尾加工至直径900mm,用于二次真空自耗重熔。One-time vacuum consumable remelting: The diameter of the crystallizer is 920mm, the consumable remelting is controlled by the melting rate, and the steady-state melting rate is controlled to 5.0kg/min; the helium cooling is started after 1500kg is melted; the current is reduced after the remaining 2000kg to adjust the melting The speed reaches 6.0kg/min; after the remaining 250kg, the heat sealing is started, and the heat sealing is controlled by the current. The primary consumable remelting ingot is machined and flat-headed to a diameter of 900mm, which is used for secondary vacuum consumable remelting.
二次真空自耗重熔:结晶器选用1050mm,熔通过熔速进行控制,稳态熔速控制为6.5kg/min;开始熔炼1500kg后启动氦气冷却;剩余3000kg后降低电流调整熔速至6.0kg/min;剩余1000kg后启动热封顶,热封顶通过电流控制。二次真空自耗重熔完成后,真空冷却5h,而后破空在2h内转移至退火炉内去应力退火,避免钢锭脱模后炸裂。退火炉应预先加热至450℃保温24h实现均温,然后以25℃/h的速度升温至900℃保温24h,而后以35℃/h的速度冷却至600℃保温12h,而后空冷,即得目标铸锭。Secondary vacuum self-consumption remelting: The mold is 1050mm, the melting is controlled by the melting rate, and the steady-state melting rate is controlled to 6.5kg/min; the helium cooling is started after 1500kg is melted; the current is reduced after the remaining 3000kg to adjust the melting rate to 6.0 kg/min; after the remaining 1000kg, the heat sealing is started, and the heat sealing is controlled by the current. After the secondary vacuum consumable remelting is completed, vacuum cooling is performed for 5 hours, and then the void is transferred to the annealing furnace for stress relief annealing within 2 hours to prevent the ingot from bursting after demolding. The annealing furnace should be preheated to 450°C for 24 hours to achieve uniform temperature, then heated at a rate of 25°C/h to 900°C for 24 hours, and then cooled at a rate of 35°C/h to 600°C for 12 hours, and then air-cooled to achieve the target Ingot casting.
试验结果:试制的706合金1050mm自耗锭,重量为15.8吨,未出现热裂,且无黑斑、白斑等冶金缺陷。对钢锭的头尾进行成分测试,测试结果表明, 头尾Al、Ti元素无明显烧损,Al元素为头部为0.16%、尾部为0.12%,Ti元素为头部为1.60%、尾部为1.46%。将直径1050mm的三次自耗重熔锭高温均匀化扩散退火处理后,车光后安排锻造,制备锻造棒材。棒材经无损探伤检验,发现电渣重熔接头处无异常信号,表明通过三次真空自耗重熔可以有效解决706合金电渣接头处的冶金质量问题。Test results: The trial-produced 1050mm consumable ingot of 706 alloy weighs 15.8 tons. There is no hot cracking and no metallurgical defects such as black spots and white spots. The composition test on the head and tail of the steel ingots shows that there is no obvious burning loss of Al and Ti elements at the head and tail. The Al element is 0.16% for the head and 0.12% for the tail. The Ti element is 1.60% for the head and 1.46 for the tail. %. After the three-time consumable remelted ingot with a diameter of 1050mm is homogenized at high temperature and diffused and annealed, it is arranged for forging after polishing to prepare forged bars. After non-destructive testing of the bar, it was found that there was no abnormal signal at the electroslag remelting joint, indicating that the three-time vacuum consumable remelting can effectively solve the metallurgical quality problem at the 706 alloy electroslag joint.
比较例Comparative example
比较例用于说明采用三联制备工艺制备706合金(直径920mm自耗锭)的制备方法。The comparative example is used to illustrate the preparation method of 706 alloy (a consumable ingot with a diameter of 920 mm) prepared by a triple preparation process.
目标706合金成分同实施例1的706合金成分(按质量百分比):The target 706 alloy composition is the same as the 706 alloy composition of Example 1 (by mass percentage):
C0.018%,Cr 15.8%,Ni 41.5%,Nb3.01%,Ti 1.72%,Al 0.25%,Si 0.02%,Mn 0.01%,P 0.006%,S 0.0006%,Co 0.02%,Mo 0.01%,B 0.004%,Cu 0.02%,Ca 0.004%,N 0.005%,O 0.002%,Fe余量。C0.018%, Cr 15.8%, Ni 41.5%, Nb3.01%, Ti 1.72%, Al 0.25%, Si 0.02%, Mn 0.01%, P 0.006%, S 0.0006%, Co 0.02%, Mo 0.01%, B 0.004%, Cu 0.02%, Ca 0.004%, N 0.005%, O 0.002%, Fe balance.
具体制备方法如下:The specific preparation method is as follows:
真空感应熔炼:根据设计的合金成分要求,按单位重量的合金所需元素称取40%返回料,剩余采用全新金属原材料。采用12吨真空感应炉制备2支直径820mm的12吨自耗锭,熔化温度上限为1550℃,熔清后检测钢液成分,通过补加新金属,控制钢液中Ni含量约42.0wt%,Nb含量约3.10wt%,Ti含量约1.82wt%,Al含量约0.35wt%,采用电磁搅拌40min;精炼温度为1480℃,出钢温度为1500℃。浇钢完成后炉冷4小时后脱模,然后直接进行退火处理。退火炉预先加热至650℃,而后以25℃/h的速度升温至900℃保温24h,而后以15℃/h的速度冷却至600℃保温10h,而后空冷。Vacuum induction smelting: According to the designed alloy composition requirements, 40% of the return material is weighed according to the required elements of the alloy per unit weight, and the rest is made of new metal raw materials. A 12-ton vacuum induction furnace is used to prepare two 12-ton consumable ingots with a diameter of 820mm. The upper melting temperature is 1550℃. After melting, the composition of the molten steel is detected. By adding new metal, the content of Ni in the molten steel is controlled to about 42.0wt%. The Nb content is about 3.10wt%, the Ti content is about 1.82wt%, and the Al content is about 0.35wt%. Electromagnetic stirring is used for 40 minutes; the refining temperature is 1480°C, and the tapping temperature is 1500°C. After pouring the steel, the furnace is cooled for 4 hours and then demoulded, and then directly subjected to annealing treatment. The annealing furnace is preheated to 650°C, and then heated to 900°C at a rate of 25°C/h for 24 hours, and then cooled to 600°C at a rate of 15°C/h for 10 hours, and then air-cooled.
将退火后的真空感应锭车光、平头尾制备电渣电极。The annealed vacuum induction ingots are turned, and the ends are flattened to prepare electroslag electrodes.
电渣重熔:结晶器选用直径1100mm,渣系选用(CaF 2-CaO-Al 2O 3-TiO 2)四元渣,具体组成为:CaF 270%,CaO15%,Al 2O 315%,TiO 2 6%。稳态熔速为10kg/min,熔炼过程中通入0.2bar压力的Ar气保护,避免熔炼过程中钢液与空气中的氧气和氮气接触。电极交换前,在剩余重量600kg时,调整输入功率和电压提高熔速,在稳态熔速基础上以0.55kg/min的斜率提高熔速,至15kg/min时保持稳定至开始交换电渣电极。交换电极过程保持交换前的冶炼参数,交换时间不能超过2min。交换电极完成后,第二支电极熔化200kg后,通过调整输入功 率和电压提高熔速,以0.75kg/min的斜率降低至10kg/min,至第二支电极剩余500kg后开始热封顶。 Electroslag remelting: The diameter of the crystallizer is 1100mm, and the slag system is (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag. The specific composition is: CaF 2 70%, CaO 15% , Al 2 O 3 15% , TiO 2 6%. The steady-state melting rate is 10kg/min, and Ar gas protection at 0.2bar pressure is introduced during the smelting process to prevent the molten steel from contacting oxygen and nitrogen in the air during the smelting process. Before electrode exchange, when the remaining weight is 600kg, adjust the input power and voltage to increase the melting rate, and increase the melting rate with a slope of 0.55kg/min on the basis of the steady-state melting rate. When it reaches 15kg/min, it will remain stable until the electroslag electrode is exchanged. . The electrode exchange process maintains the smelting parameters before the exchange, and the exchange time cannot exceed 2 min. After the electrode exchange is completed, after the second electrode melts 200kg, the melting rate is increased by adjusting the input power and voltage, and the melting rate is reduced to 10kg/min at a slope of 0.75kg/min. When the second electrode remains 500kg, the heat sealing starts.
电渣重熔结束后应在炉内水冷结晶器中通水冷却4h,脱模后0.5h内转移至退火炉内去应力退火。退火炉应预先加热至450℃,在450℃保温24h,然后以15℃/h的速度升温至650℃保温4h,而后以25℃/h的速度升温至950℃保温12h,而后以15℃/h的速度冷却至600℃保温12h,而后空冷。After the electroslag remelting is completed, it should be cooled by passing water in a water-cooled crystallizer in the furnace for 4 hours, and transferred to the annealing furnace for stress relief annealing within 0.5 hours after demolding. The annealing furnace should be preheated to 450°C, kept at 450°C for 24h, then at a rate of 15°C/h to 650°C for 4h, then at a rate of 25°C/h to 950°C for 12h, and then at 15°C/h Cool down to 600°C for 12 hours at a rate of h, then cool in air.
电渣锭高温扩散退火:在550℃以下温度装炉保温4h,而后以10℃/h的速度升温至950℃,而后以15℃/h的速度升温至1100℃保温12h,而后以20℃/h的速度升温至1190℃保温48h,而后以15℃/h的速度冷却至850℃保温24h,而后空冷。High temperature diffusion annealing of electroslag ingots: install the furnace at a temperature below 550°C for 4 hours, then heat up to 950°C at a rate of 10°C/h, then heat up to 1100°C at a rate of 15°C/h, hold for 12 hours, and then at 20°C/h The temperature was raised to 1190°C for 48 hours at a rate of h, and then cooled to 850°C for 24 hours at a rate of 15°C/h, and then air-cooled.
电极锻制:直径1100mm电渣锭的锻前加热温度选用1150℃,锻前加热时间为10h。自由锻采用3500吨快锻机单向拔长,每道次单边压下量控制为25mm,终锻温度为900℃,最终经锻制、车光、平头尾制备为直径820mm自耗电极。Electrode forging: The heating temperature before forging of the electroslag ingot with a diameter of 1100mm is 1150℃, and the heating time before forging is 10h. The free forging adopts a 3500 ton fast forging machine to draw the length in one direction. The unilateral reduction of each pass is controlled to 25mm, and the final forging temperature is 900℃. The consumable electrode with a diameter of 820mm is finally prepared by forging, turning, and flat head. .
自耗重熔:结晶器选用直径920mm,自耗重熔通过熔速进行控制,稳态熔速控制为5.5kg/min;开始熔炼1000kg后启动氦气冷却;剩余2000kg后降低电流调整熔速至4.0kg/min;剩余500kg后启动热封顶,热封顶通过电流控制。自耗重熔完成后,真空冷却3h,而后破空在2h内转移至退火炉内去应力退火,避免钢锭脱模后炸裂。退火炉应预先加热至450℃保温8h实现均温,然后以10℃/h的速度升温至850℃保温24h,而后以15℃/h的速度冷却至600℃保温12h,而后空冷。Self-consumable remelting: The diameter of the crystallizer is 920mm, and the self-consumable remelting is controlled by the melting rate. The steady-state melting rate is controlled at 5.5kg/min; the helium cooling is started after the smelting of 1000kg; after the remaining 2000kg, the current is reduced to adjust the melting rate to 4.0kg/min; after the remaining 500kg, the heat sealing is started, and the heat sealing is controlled by the current. After the consumable remelting is completed, it is cooled in vacuum for 3 hours, and then the void is transferred to the annealing furnace for stress relief annealing within 2 hours to prevent the ingot from bursting after demoulding. The annealing furnace should be preheated to 450°C for 8 hours to achieve uniform temperature, and then heated at a rate of 10°C/h to 850°C for 24 hours, and then cooled at a rate of 15°C/h to 600°C for 12 hours, and then air-cooled.
试验结果:采用三联冶炼工艺试制的706合金920mm自耗锭,重量为15.2吨,未出现热裂;对钢锭的头尾进行成分测试,测试结果表明,头尾Al、Ti元素烧损明显,Al元素为头部0.29%、尾部0.19%,Ti元素为头部1.62%、尾部1.80%。将直径920mm的二次自耗锭高温均匀化扩散退火处理后,车光后安排锻造,制备锻造棒材。棒材经无损探伤检验,发现电渣重熔接头处有异常信号,解剖发现接头处存在明显的黑斑缺陷。Test results: 706 alloy 920mm consumable ingots trial-produced by the triple smelting process, weighing 15.2 tons, and no hot cracking; the composition test on the head and tail of the steel ingot, the test results show that the head and tail Al and Ti elements burned significantly, and Al The element is 0.29% in the head and 0.19% in the tail, and the Ti element is 1.62% in the head and 1.80% in the tail. After the secondary consumable ingot with a diameter of 920mm is homogenized, diffused and annealed at high temperature, it is polished and forged to prepare forged bars. The bars were inspected by non-destructive flaw detection, and abnormal signals were found at the electroslag remelting joints, and an obvious black spot defect was found at the joints after anatomy.
本具体实施例仅仅是对本发明的解释,其并不是对本发明的限制,本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改,但只要在本发明的权利要求范围内都受到专利法的保护。This specific embodiment is only an explanation of the present invention, and is not a limitation of the present invention. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contribution as needed, but as long as the rights of the present invention The scope of the requirements is protected by the patent law.

Claims (10)

  1. 一种大尺寸高铌高温706合金铸锭,其特征在于,所述高铌高温合金大尺寸铸锭为直径在800mm以上,按质量百分比计,所述大尺寸高铌高温706合金铸锭的化学成分为:A large-size high-niobium high-temperature 706 alloy ingot, characterized in that the large-size high-niobium high-temperature alloy ingot has a diameter of more than 800mm, and the chemical composition of the large-size high-niobium high-temperature 706 alloy ingot is calculated by mass percentage. The ingredients are:
    C≤0.02wt%,Cr 15.5~16.5wt%,Ni 40.0~43.0wt%,Nb 2.8~3.2wt%,Ti 1.5~1.8wt%,Al 0.1~0.3wt%,Si≤0.10wt%,Mn≤0.20wt%,P≤0.015wt%,S≤0.0013wt%,Co≤0.30wt%,Mo≤0.20wt%,B≤0.006wt%,Cu≤0.30wt%,Ca≤0.005wt%,N≤0.006wt%,O≤0.005wt%,Fe余量。C≤0.02wt%, Cr 15.5~16.5wt%, Ni 40.0~43.0wt%, Nb 2.8~3.2wt%, Ti 1.5~1.8wt%, Al 0.1~0.3wt%, Si≤0.10wt%, Mn≤0.20 wt%, P≤0.015wt%, S≤0.0013wt%, Co≤0.30wt%, Mo≤0.20wt%, B≤0.006wt%, Cu≤0.30wt%, Ca≤0.005wt%, N≤0.006wt% , O≤0.005wt%, Fe balance.
  2. 权利要求1所述的一种大尺寸高铌高温706合金铸锭的冶炼工艺,其特征在于,包括以下步骤:The smelting process of a large-size high-niobium high-temperature 706 alloy ingot according to claim 1, characterized in that it comprises the following steps:
    真空感应熔炼:根据设计的合金成分要求,按单位重量的合金所需元素称取纯金属原材料和/或返回料为原料,进行真空感应熔炼,控制熔炼母液中Ni含量为40.0~43.0wt%,Nb含量为2.80~3.3wt%,Ti含量为0.5~2.0wt%,Al含量为0.2~0.5wt%,浇注多支成分相同的真空感应锭;Vacuum induction smelting: According to the designed alloy composition requirements, the pure metal raw materials and/or return materials are weighed according to the required elements of the alloy per unit weight as raw materials, and vacuum induction smelting is performed to control the Ni content in the smelting mother liquor to 40.0-43.0wt%. Nb content is 2.80~3.3wt%, Ti content is 0.5~2.0wt%, Al content is 0.2~0.5wt%, and multiple vacuum induction ingots with the same composition are poured;
    交换电渣重熔:利用所制成的真空感应锭制得相同数量的电渣电极;采用所有制得的电渣电极,氩气保护状态下进行交换电渣重熔,所采用的渣系为(CaF 2-CaO-Al 2O 3-TiO 2)四元渣,(CaF 2-CaO-Al 2O 3-TiO 2)四元渣中CaF 2占60~75wt%,CaO占10~25wt%,Al 2O 3占8~13wt%,TiO 2占1~10wt%;交换电渣重熔结束后,冷却,脱模,制得电渣锭: Exchange electroslag remelting: the same number of electroslag electrodes are prepared by using the vacuum induction ingots made; all the prepared electroslag electrodes are used, and the exchange electroslag remelting is performed under argon protection. The slag system used is ( CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag, (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag contains 60~75wt% of CaF 2 and 10~25wt% of CaO. Al 2 O 3 accounts for 8 to 13 wt%, and TiO 2 accounts for 1 to 10 wt%; after the exchange electroslag remelting is completed, it is cooled and demolded to obtain an electroslag ingot:
    一次真空自耗重熔:对脱模的电渣锭进行一次退火、二次退火、锻造拔长至预定尺寸,制得一次自耗电极,其中二次退火温度高于一次退火温度;然后利用一次自耗电极进行一次真空自耗重熔;Primary vacuum consumable remelting: the demolded electroslag ingot is subjected to primary annealing, secondary annealing, forging and drawing to a predetermined size to obtain a primary consumable electrode, wherein the secondary annealing temperature is higher than the primary annealing temperature; then use A consumable electrode is remelted once in vacuum;
    二次真空自耗重熔:对一次真空自耗重熔所得的一次自耗重熔锭,车光、平头尾,得到二次自耗电极;然后利用二次自耗电极进行二次真空自耗重熔,制备目标直径的铸锭。Secondary vacuum consumable remelting: the primary consumable remelted ingots obtained by the primary vacuum consumable remelting, car light, flat head and tail, to obtain a secondary consumable electrode; then use the secondary consumable electrode for secondary vacuum Consumable remelting to prepare ingots of target diameter.
  3. 根据权利要求2所述的冶炼工艺,其特征在于,真空感应熔炼步骤中,熔化温度为1300~1550℃,原料熔清后,在电磁搅拌作用下精炼15~120min,精炼温度为1350~1550℃;然后冷却1~10小时后,脱模,得真空感应锭;重复多次该真空感应熔炼过程,得多支成分相同的真空感应锭。The smelting process according to claim 2, characterized in that, in the vacuum induction melting step, the melting temperature is 1300-1550°C, after the raw materials are melted, refining is carried out under electromagnetic stirring for 15-120 minutes, and the refining temperature is 1350-1550°C. ; Then, after cooling for 1-10 hours, demoulding to obtain a vacuum induction ingot; repeat the vacuum induction melting process many times to have multiple vacuum induction ingots with the same composition.
  4. 根据权利要求2所述的冶炼工艺,其特征在于,制备电渣电极的方式为,对 每支真空感应锭直接去应力退火,退火时,预先升温至600~800℃,而后以5~45℃/h的速度升温至800~1000℃并保温4~32h,而后以1~35℃/h的速度冷却至600~800℃保温4~32h,而后空冷,然后再车光、平头尾,即得电渣电极。The smelting process according to claim 2, characterized in that the method of preparing the electroslag electrode is directly stress-relieving annealing for each vacuum induction ingot. During annealing, the temperature is pre-heated to 600-800°C, and then the temperature is 5 to 45°C. Heat up to 800~1000℃ and keep it warm for 4~32h at a rate of 1~35℃/h, then cool to 600~800℃ and keep it for 4~32h at a rate of 1~35℃/h, then air cooling, and then car light, flat head and tail, that is Electroslag electrode.
  5. 根据权利要求2所述的冶炼工艺,其特征在于,进行交换电渣重熔时,所采用的渣系为(CaF 2-CaO-Al 2O 3-TiO 2)四元渣,(CaF 2-CaO-Al 2O 3-TiO 2)四元渣中CaF 2占60~75wt%,CaO占10~25wt%,Al 2O 3占8~13wt%,TiO 2占1~5wt%。 The smelting process according to claim 2, characterized in that when performing exchange electroslag remelting, the slag system used is (CaF 2 -CaO-Al 2 O 3 -TiO 2 ) quaternary slag, (CaF 2- (CaO-Al 2 O 3 -TiO 2 ) In the quaternary slag, CaF 2 accounts for 60 to 75 wt %, CaO accounts for 10 to 25 wt %, Al 2 O 3 accounts for 8 to 13 wt %, and TiO 2 accounts for 1 to 5 wt %.
  6. 根据权利要求5所述的冶炼工艺,其特征在于,电渣重熔的稳态熔速控制为5~15kg/min;并且,每次电极交换前,当前一支电极剩余重量500kg~1000kg时,在稳态熔速基础上以0.5~2kg/min的斜率提高熔速至12~25kg/min时,保持稳定至开始交换电渣电极,且交换电极过程保持交换前的冶炼参数,交换时间不超过2min;每次电极交换完成后,当后一支电极熔化100kg~500kg后,以0.5~2kg/min的斜率降低熔速至稳态熔速5~15kg/min,继续重熔,至最后一支电极剩余200~600kg后开始热封顶;交换电渣重熔结束后,冷却2~10h,脱模,得电渣锭。The smelting process according to claim 5, characterized in that the steady-state melting rate of electroslag remelting is controlled to be 5-15kg/min; and, before each electrode exchange, when the remaining weight of the current electrode is 500kg-1000kg, On the basis of the steady-state melting rate, increase the melting rate to 12-25kg/min with a slope of 0.5-2kg/min, keep it stable until the electroslag electrode is exchanged, and the electrode exchange process maintains the smelting parameters before the exchange, and the exchange time does not exceed 2min; After each electrode exchange is completed, when the next electrode melts 100kg~500kg, reduce the melting rate with a slope of 0.5~2kg/min to a steady state melting rate of 5~15kg/min, continue to remelt until the last one After the remaining 200-600kg of the electrode is left, heat-sealing starts; after the exchange of electroslag remelting, it is cooled for 2-10h, demolded, and an electroslag ingot is obtained.
  7. 根据权利要求2所述的冶炼工艺,其特征在于,进行多次真空自耗重熔步骤中,对脱模的电渣锭进行一次退火、二次退火、锻造拔长至预定尺寸以制得一次自耗电极的具体实现方式如下,The smelting process according to claim 2, characterized in that, in performing multiple vacuum consumable remelting steps, the demolded electroslag ingot is subjected to primary annealing, secondary annealing, and forging to a predetermined size to obtain a primary The concrete realization of the consumable electrode is as follows,
    对电渣锭,在脱模后0.5~2h内启动一次退火,具体为,预先加热至300~550℃,保温12~32h实现均温,然后以1~25℃/h的速度升温至600~750℃保温4~32h,而后以5~35℃/h的速度升温至800~1000℃保温4~32h,而后以1~35℃/h的速度冷却至550~750℃保温4~32h,而后空冷;For electroslag ingots, an annealing is started within 0.5-2h after demolding. Specifically, it is preheated to 300-550℃, held for 12-32h to achieve uniform temperature, and then heated at a rate of 1-25℃/h to 600~ Hold at 750°C for 4~32h, then heat up to 800~1000°C at a rate of 5~35℃/h and keep it at 800~1000℃ for 4~32h, then cool to 550~750℃ at a rate of 1~35℃/h and keep it at 4~32h, then Air cooling
    对一次退火完成后的电渣锭进行二次退火,具体为,以5~35℃/h的速度升温至800~1000℃,而后以1~25℃/h的速度升温至1050~1150℃保温4~32h,而后以1~25℃/h的速度升温至1150~1250℃保温24~72h,而后以1~35℃/h的速度冷却至800~950℃保温4~32h,而后空冷;Perform secondary annealing on the electroslag ingot after primary annealing, specifically, heating up to 800-1000°C at a rate of 5 to 35°C/h, and then heating up to 1050 to 1150°C at a rate of 1 to 25°C/h 4~32h, then heat up at a rate of 1~25℃/h to 1150~1250℃ and keep for 24~72h, then cool at a rate of 1~35℃/h to 800~950℃ and keep it for 4~32h, then air cooling;
    对二次退火后电渣锭,在锻前加热至1100~1180℃,锻前加热时间为4~12h,自由锻采用3000吨以上的快锻机单向拔长,每道次单边压下量控制为5~30mm,终锻温度为850~1000℃;For the electroslag ingot after secondary annealing, it is heated to 1100~1180℃ before forging, and the heating time before forging is 4~12h. The free forging adopts a fast forging machine of more than 3000 tons to draw the length in one direction, and each pass is pressed down on one side. The amount is controlled at 5~30mm, and the final forging temperature is 850~1000℃;
    对自由锻拔长之后的钢锭,车光、平头尾,得到一次自耗电极。For the steel ingot after free forging and drawing, the head and tail are flattened, and a consumable electrode is obtained.
  8. 根据权利要求2所述的冶炼工艺,其特征在于,进行一次真空自耗重熔时,稳态熔速控制为3.5~7.5kg/min;开始熔炼800~2000kg后启动氦气冷却;剩余1500~5000kg后降低电流调整熔速至3.0~7.0kg/min;剩余200~1000kg后启动热封顶,制得一次自耗重熔锭。The smelting process according to claim 2, characterized in that when performing a vacuum consumable remelting, the steady-state melting rate is controlled to be 3.5~7.5kg/min; the helium cooling is started after 800~2000kg smelting is started; the remaining 1500~ After 5000kg, the current is reduced to adjust the melting rate to 3.0~7.0kg/min; after the remaining 200~1000kg, the heat sealing is started to obtain a self-consumable remelting ingot.
  9. 根据权利要求2所述的冶炼工艺,其特征在于,进行二次真空自耗重熔时,稳态熔速控制为4.0~8.5kg/min;开始熔炼1000~3000kg后通入氦气冷却;剩余2000~5500kg后降低电流调整熔速至3.0~7.5kg/min;剩余250~1500kg后启动热封顶。The smelting process according to claim 2, characterized in that when performing secondary vacuum consumable remelting, the steady-state melting rate is controlled to be 4.0-8.5kg/min; after the smelting starts, 1000-3000kg is passed through helium for cooling; After 2000~5500kg, reduce the current to adjust the melting rate to 3.0~7.5kg/min; after the remaining 250~1500kg, start heat sealing.
  10. 根据权利要求2所述的冶炼工艺,其特征在于,二次自耗重熔完成后,真空冷却1~8h,而后在2h内启动去应力退火;退火时,预先加热至300~750℃,保温4~32h实现均温,然后以5~50℃/h的速度升温至800~1000℃,保温4~32h,而后以1~35℃/h的速度冷却至550~750℃保温4~32h,而后空冷,即得目标直径的铸锭。The smelting process according to claim 2, characterized in that, after the secondary consumable remelting is completed, vacuum cooling is performed for 1 to 8 hours, and then stress relief annealing is started within 2 hours; during annealing, it is preheated to 300 to 750°C and kept warm. Achieve uniform temperature in 4~32h, then heat up to 800~1000℃ at a rate of 5~50℃/h, keep it for 4~32h, then cool to 550~750℃ at a rate of 1~35℃/h and keep it for 4~32h, Then, air cooling is used to obtain an ingot of the target diameter.
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