CN117363960B - Low-carbon aluminum-free high-niobium-iron-based superalloy and preparation method thereof - Google Patents

Low-carbon aluminum-free high-niobium-iron-based superalloy and preparation method thereof Download PDF

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CN117363960B
CN117363960B CN202311677682.5A CN202311677682A CN117363960B CN 117363960 B CN117363960 B CN 117363960B CN 202311677682 A CN202311677682 A CN 202311677682A CN 117363960 B CN117363960 B CN 117363960B
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equal
alloy
iron
niobium
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CN117363960A (en
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蒋世川
周扬
韩福
陈琦
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Chengdu Advanced Metal Materials Industry Technology Research Institute Co Ltd
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Chengdu Advanced Metal Materials Industry Technology Research Institute Co Ltd
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C22C33/06—Making ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
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    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
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    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10—Handling in a vacuum
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    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
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    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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    • C22C—ALLOYS
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    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
    • C21C2007/0018—Boron

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Abstract

The invention relates to the field of vacuum smelting of high-temperature alloy, in particular to a low-carbon aluminum-free high-niobium-iron-based high-temperature alloy and a preparation method thereof, wherein the preparation method comprises the following steps: and (3) a batching procedure: selecting high-purity graphite, single crystal Si, ferroboron, metal Nb, metal Ti, ni-Mg alloy, ni plate, co plate and pure Fe, proportioning according to the mass percentage of preset chemical components, controlling the total oxygen content in raw materials to be lower than a first preset value, controlling the nitrogen content to be lower than a second preset value, and carrying out a charging process, a melting process, a refining process, a deoxidizing alloying process and a casting process. By adopting the technical scheme, the invention can solve the problem of smelting the ultralow oxygen and nitrogen content of the low-carbon aluminum-free high-niobium-iron-based high-temperature alloy in a large vacuum induction furnace, can produce the high-purity purification vacuum induction ingot with the oxygen content less than or equal to 0.0008% and the nitrogen content less than or equal to 0.0008%, meets the requirement of the alloy on purity in severe use environment, and improves the comprehensive performance and stability of the product.

Description

Low-carbon aluminum-free high-niobium-iron-based superalloy and preparation method thereof
Technical Field
The invention relates to the field of vacuum smelting of high-temperature alloy, in particular to a low-carbon aluminum-free high-niobium-iron-based high-temperature alloy and a preparation method thereof.
Background
The high-temperature alloy is a kind of metal material which takes a plurality of elements such as iron, nickel, cobalt, chromium and the like as a matrix, is strengthened by solid solution of tungsten, molybdenum and the like, is strengthened by precipitation of gamma ', gamma', titanium and the like, can work for a long time under the action of high temperature above 600 ℃ and certain stress, and is widely applied to high-end parts such as turbine discs, combustion chambers, blades, cases, fasteners and the like of aeroengines and industrial gas turbines. Wherein GH2909 is a precipitation hardening type deformation superalloy, and the use temperature is below 650 ℃. The alloy has high strength, high cold and hot fatigue resistance, low expansion coefficient and constant elastic modulus, and good hot working plasticity, cold forming and welding performance, and is widely applied to a rear casing, a bearing ring, a heat insulation ring, a combustion chamber sealing ring, a honeycomb seat, a turbine outer ring and the like of a high-pressure compressor of a turbine engine, a thrust combustion chamber of a rocket engine, an exhaust duct, a collecting box and the like. The alloy has high purity requirement because of the harsh use environment. Oxygen is used as a harmful impurity element in the superalloy, oxide inclusions are easily formed with oxygen-philic metal elements, nitride inclusions are formed when the nitrogen content is high, the inclusions are difficult to eliminate in the later smelting or heat treatment process, and the inclusions are easily used as crack initiation sources and crack propagation channels in the service process of the superalloy, so that the core mechanical properties such as durability, fatigue, creep and the like of the superalloy can be reduced. A great deal of researches show that reducing the content of oxygen, nitrogen and inclusions in the alloy, improving the purity, and being an important strategy for improving the comprehensive performance and stability of the high-temperature alloy.
In order to ensure that the actual requirement of product performance controls C to be less than or equal to 0.03 percent, so that the carbon deoxidization and denitrification effect in the vacuum smelting process is poor, a large vacuum induction furnace is used, a molten steel pool is deep, the ferrostatic pressure is high, the carbon content is low, the density is low, the ferrostatic pressure floats on the surface of alloy liquid to be difficult to achieve good deoxidization and denitrification effect, the alloy liquid contains 4.3-5.2 percent of Nb and 1.3-1.80 percent of Ti, and due to the limitation and the deficiency of the existing production process, the oxygen content in the metal Nb is 300-1500 PPm, the nitrogen content is 130-430 PPm and a large amount of Al 2 O 3 The inclusion contains 400-800 PPm of oxygen and 30-100 PPm of nitrogen in the sponge Ti; the metal Nb and sponge Ti raw materials required by smelting contain a large amount of oxygen and nitrogen contents and oxide impurities, the fluctuation is large, nb and Ti elements can reduce the vacuum carbon deoxidization effect at a certain time of smelting vacuum degree and temperature, the solubility of nitrogen in alloy liquid is increased, the vacuum denitrification is not facilitated, the purity of the product is difficult to control, and the removal effect of deoxidizer Al is not obvious on gas. In the prior art, the alloy adopts the technologies of batch-wise carbon adding, high-temperature refining and the like in the vacuum smelting process, and has no effect of removing oxygen and nitrogen from the alloyObvious.
Based on this, the prior art still remains to be improved.
Disclosure of Invention
In view of the above, the embodiment of the invention aims to provide a low-carbon aluminum-free high-niobium-iron-based superalloy and a preparation method thereof, and by using the technical scheme of the invention, the difficult problem of smelting the ultralow oxygen and nitrogen content of a large vacuum induction furnace of the low-carbon aluminum-free high-niobium-iron-based superalloy can be solved, and a high-purity vacuum induction ingot with the oxygen content less than or equal to 0.0008% and the nitrogen content less than or equal to 0.0008% can be produced, so that the requirement of the alloy on purity in severe use environment is met, and the comprehensive performance and stability of the product are improved.
Based on the above object, an aspect of the embodiment of the present invention provides a method for preparing a low-carbon aluminum-free high-niobium-iron-based superalloy, including the steps of:
and (3) a batching procedure: selecting high-purity graphite, single crystal Si, ferroboron, metal Nb, metal Ti, ni-Mg alloy, ni plate, co plate and pure Fe, proportioning according to the mass percentage of preset chemical components, and controlling the total oxygen content in raw materials to be lower than a first preset value and the nitrogen content to be lower than a second preset value;
and (3) charging: charging the raw materials according to two batches under vacuum after the material proportioning is finished;
and (3) a melting procedure: after the charging is completed, power transmission melting is started under the condition that the vacuum degree is a third preset value, the first batch of raw materials are melted and then stirred for a first preset time at preset power frequency, and the second batch of raw materials are melted and then stirred for the first preset time at preset power frequency;
refining: after stirring is finished, controlling the vacuum degree in the refining period to be a fourth preset value, and transmitting electricity and heating to a fifth preset value to refine for a second preset time;
deoxidizing and alloying process: adding monocrystalline Si to remove residual gas content in alloy liquid after refining, adding metal Ti to carry out alloying, then transmitting power, heating to a sixth preset value, stirring and preserving heat for a third preset time, charging argon, adding ferroboron, then adding Ni-Mg alloy to carry out deoxidization and stirring;
casting procedure: and tapping with electricity, wherein the casting temperature is a seventh preset value.
According to one embodiment of the invention, in the batching process, raw materials are prepared according to the proportion of C less than or equal to 0.03%, mn less than or equal to 1%, si:0.25-0.5%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, cu is less than or equal to 0.5%, B is less than or equal to 0.012%, mo is less than or equal to 0.2%, al is less than or equal to 0.2%, cr is less than or equal to 1%, nb:4.3-5.2%, ti:1.3-1.80%, ni:35-40%, co:12-16%, and the balance of Fe, and controlling the total oxygen content of the raw materials to be less than or equal to 0.02% and the nitrogen content to be less than or equal to 0.002%.
According to one embodiment of the invention, in the charging process, a first batch is sequentially charged with half of Ni plate, all high purity graphite, all metallic Nb, half of Co plate, half of pure Fe, a second batch is charged with the rest of Ni plate, the rest of Co plate, the rest of pure Fe, all single crystal Si and metallic Ti are sequentially charged after refining is completed, and all ferroboron and Ni-Mg alloy are sequentially charged after argon is charged.
According to one embodiment of the invention, in the melting process, three-stage pump vacuum pumping is adopted after the charging is completed, power transmission melting is started under the condition that the vacuum degree is less than or equal to 0.5Pa, the power transmission power of the first 30 mm is 300-500Kw, then the power transmission is carried out by adopting the power transmission power of 1300-1700Kw, the power transmission power is reduced to 800-1200Kw after an alloy liquid molten pool is formed, 100Kw power frequency stirring is adopted for 30min after the first raw material is melted, and 100Kw power frequency stirring is adopted for 30min after the second raw material is melted.
According to one embodiment of the invention, in the refining process, the vacuum degree is controlled to be less than or equal to 0.1Pa in the refining period, the power is transmitted and the temperature is increased to 1450-1470 ℃ for refining, and the refining time is 20-50min.
According to one embodiment of the invention, in the deoxidizing alloying process, the vacuum degree is controlled to be less than or equal to 0.1Pa, the residual gas content in the alloy liquid is removed by adding monocrystalline Si, then metal Ti is added for alloying, then power is transmitted, the temperature is raised to 1450-1470 ℃, stirring and heat preservation are carried out for 30min, then 30000Pa of argon is filled, and then ferroboron and 0.02kg/t are added in sequence Alloy The Ni-Mg alloy of (C) was stirred for 5min.
According to one embodiment of the invention, in the casting process, the charged steel is tapped at a casting temperature of 1450-1470 ℃.
According to one embodiment of the invention, a low carbon aluminum-free high niobium-iron-based superalloy is prepared in a 12 ton vacuum induction furnace.
Another aspect of the embodiment of the invention provides a low-carbon aluminum-free high-niobium-iron-based superalloy, comprising the following components in percentage by mass:
c is less than or equal to 0.03 percent, mn is less than or equal to 1 percent, si:0.25-0.5%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, cu is less than or equal to 0.5%, B is less than or equal to 0.012%, mo is less than or equal to 0.2%, cr is less than or equal to 1%, nb:4.3-5.2%, ti:1.3-1.80%, ni:35-40%, co:12-16%, and the balance of Fe and unavoidable impurities.
According to one embodiment of the invention, the content of oxygen in the unavoidable impurities is less than or equal to 0.0008% and the content of nitrogen is less than or equal to 0.0008% in mass percent.
The invention has the following beneficial technical effects: the preparation method of the low-carbon aluminum-free high-niobium-iron-based superalloy provided by the embodiment of the invention comprises the following steps of: selecting high-purity graphite, single crystal Si, ferroboron, metal Nb, metal Ti, ni-Mg alloy, ni plate, co plate and pure Fe, proportioning according to the mass percentage of preset chemical components, and controlling the total oxygen content in raw materials to be lower than a first preset value and the nitrogen content to be lower than a second preset value; and (3) charging: charging the raw materials according to two batches under vacuum after the material proportioning is finished; and (3) a melting procedure: after the charging is completed, power transmission melting is started under the condition that the vacuum degree is a third preset value, the first batch of raw materials are melted and then stirred for a first preset time at preset power frequency, and the second batch of raw materials are melted and then stirred for the first preset time at preset power frequency; refining: after stirring is finished, controlling the vacuum degree in the refining period to be a fourth preset value, and transmitting electricity and heating to a fifth preset value to refine for a second preset time; deoxidizing and alloying process: adding monocrystalline Si to remove residual gas content in alloy liquid after refining, adding metal Ti to carry out alloying, then transmitting power, heating to a sixth preset value, stirring and preserving heat for a third preset time, charging argon, adding ferroboron, then adding Ni-Mg alloy to carry out deoxidization and stirring; casting procedure: according to the technical scheme that the charged tapping is carried out, and the casting temperature is a seventh preset value, the problem of smelting the ultralow oxygen and nitrogen content of a large vacuum induction furnace with low carbon, no aluminum and high niobium-iron-based superalloy can be solved, a high-purity purification vacuum induction ingot with the oxygen content less than or equal to 0.0008% and the nitrogen content less than or equal to 0.0008% can be produced, the requirement of the alloy on purity in a severe use environment is met, and the comprehensive performance and stability of the product are improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are necessary for the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention and that other embodiments may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a method for preparing a low-carbon aluminum-free high-niobium-iron-based superalloy according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments of the present invention will be described in further detail with reference to the accompanying drawings.
It should be understood that the embodiments of the invention shown in the exemplary embodiments are only illustrative. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art will readily appreciate that many modifications are possible without materially departing from the teachings of the subject matter of this disclosure. Accordingly, all such modifications are intended to be included within the scope of present invention. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and parameters of the exemplary embodiments without departing from the spirit of the present inventions.
In view of the above, the first aspect of the embodiments of the present invention provides an embodiment of a method for preparing a low-carbon aluminum-free high-niobium-iron-based superalloy. Fig. 1 shows a schematic flow chart of the method.
As shown in fig. 1, the method may include the steps of:
s1, a batching process: selecting high-purity graphite, single crystal Si, ferroboron, metal Nb, metal Ti, ni-Mg alloy, ni plate, co plate and pure Fe, proportioning according to the mass percentage of preset chemical components, and controlling the total oxygen content in raw materials to be lower than a first preset value and the nitrogen content to be lower than a second preset value. The raw materials are mixed according to the proportion that C is less than or equal to 0.03 percent, mn is less than or equal to 1 percent, si:0.25-0.5%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, cu is less than or equal to 0.5%, B is less than or equal to 0.012%, mo is less than or equal to 0.2%, al is less than or equal to 0.2%, cr is less than or equal to 1%, nb:4.3-5.2%, ti:1.3-1.80%, ni:35-40%, co:12-16%, and the balance of Fe, and controlling the total oxygen content of the raw materials to be less than or equal to 0.02% and the nitrogen content to be less than or equal to 0.002%.
S2, charging procedure: after the dosing is completed, the raw materials are charged in two batches under vacuum. The first batch is sequentially added with half of Ni plate, all high-purity graphite, all metal Nb, half of Co plate and half of pure Fe, the second batch is added with the rest of Ni plate, rest of Co plate and rest of pure Fe, all single crystal Si and metal Ti are sequentially added after refining is finished, and all ferroboron and Ni-Mg alloy are sequentially added after argon is filled.
S3, melting procedure: and after the charging is completed, power transmission melting is started under the condition that the vacuum degree is a third preset value, the first preset time is adopted for stirring at the preset power frequency after the first batch of raw materials are melted, and the first preset time is adopted for stirring at the preset power frequency after the second batch of raw materials are melted. And after the charging is finished, adopting a three-stage pump to vacuumize, starting to transmit power and melt under the condition that the vacuum degree is less than or equal to 0.5Pa, transmitting power at the front 30 mm by 300-500Kw, transmitting power at the front 1300-1700Kw, reducing the transmitted power to 800-1200Kw after an alloy liquid molten pool is formed, adopting 100Kw power frequency stirring for 30min after the first batch of raw materials are melted, and adopting 100Kw power frequency stirring for 30min after the second batch of raw materials are melted.
S4 refining: and after the stirring is finished, controlling the vacuum degree in the refining period to be a fourth preset value, and transmitting electricity and heating to a fifth preset value to refine for a second preset time. Controlling the vacuum degree in the refining period to be less than or equal to 0.1Pa, and heating to 1450-1470 ℃ for refining for 20-50min.
S5 deoxidizing and alloying process: after refining, adding monocrystalline Si to remove residual gas content in alloy liquid, adding metal Ti to carry out alloying, then transmitting power, heating to a sixth preset value, stirring and preserving heatAnd thirdly, after argon is filled in, ferroboron is added, and then Ni-Mg alloy is added for deoxidization and stirring. Controlling the vacuum degree to be less than or equal to 0.1Pa, adding monocrystalline Si to remove the residual gas content in the alloy liquid, adding metal Ti to carry out alloying, then sending power, heating to 1450-1470 ℃, stirring and preserving heat for 30min, then charging 30000Pa of argon, and then sequentially adding ferroboron and 0.02kg/t Alloy The Ni-Mg alloy of (C) was stirred for 5min.
S6, casting: and tapping with electricity, wherein the casting temperature is a seventh preset value. The casting temperature is 1450-1470 ℃.
By using the technical scheme of the invention, the difficult problem of smelting the ultralow oxygen and nitrogen content of the low-carbon aluminum-free high-niobium-iron-based high-temperature alloy large vacuum induction furnace can be solved, the high-purity purification vacuum induction ingot with the oxygen content less than or equal to 0.0008% and the nitrogen content less than or equal to 0.0008% can be produced, the requirement of the harsh use environment of the alloy on the purity is met, and the comprehensive performance and stability of the product are improved.
In a preferred embodiment of the present invention, in the material preparing process, the raw materials are mixed according to the proportion of C less than or equal to 0.03%, mn less than or equal to 1%, si:0.25-0.5%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, cu is less than or equal to 0.5%, B is less than or equal to 0.012%, mo is less than or equal to 0.2%, al is less than or equal to 0.2%, cr is less than or equal to 1%, nb:4.3-5.2%, ti:1.3-1.80%, ni:35-40%, co:12-16%, and the balance of Fe, and controlling the total oxygen content of the raw materials to be less than or equal to 0.02% and the nitrogen content to be less than or equal to 0.002%. Selecting high-purity graphite, single crystal Si, ferroboron, metal Nb, metal Ti, ni-Mg alloy, ni plate, co plate, pure Fe and other raw materials, carrying out surface treatment, and then carrying out batching according to the chemical component requirements of the low-carbon aluminum-free high-niobium-iron-based superalloy GH2909, namely batching according to the mass percentage, wherein the requirements of analyzing the purity of oxygen, nitrogen and the like of various raw materials are required to be carried out, and obtaining that the total carried oxygen and nitrogen content of all raw materials are respectively recorded as T O total 、T N total And control T O total ≤0.02%、T N total Less than or equal to 0.002%, T carried in by raw materials must be controlled O total 、T N total The content is because if the raw material is brought into excessive gas elements, the residual oxygen and nitrogen content in the alloy liquid after the melting and refining are higher, a great amount of nonmetallic inclusion formed in the deoxidizing alloying process remains in the alloy liquid and cannot be realizedPurifying and smelting. The high-purity graphite is selected for carbon matching, so that the high gas content brought by raw materials such as graphite electrodes and the like is reduced, the carbon matching amount is higher than the chemical composition control requirement of GH2909, the sufficient carbon matching amount is controlled, the carbon content is ensured to meet the requirement, the sufficient carbon is ensured to react with oxygen under the vacuum condition for deoxidization and oxide inclusion in the reduced alloy liquid, and the carbon matching amount is controlled according to the following formula: carbon distribution= (alloy target carbon content +3/4*T) O total ) The Ti element is 0.9, the metal Ti which is produced by vacuum consumable remelting and degassing of the sponge Ti is used as the raw material, because the Ti is an active metal element and is added in the later period of smelting, the metal Ti is used for replacing the sponge Ti, the influence of the raw material on the purity of molten steel after adding the Ti can be reduced, and 0.02kg/t is added Alloy The Ni-Mg alloy of the formula (I) utilizes Mg to remove the oxygen content remained in molten steel, thereby being beneficial to realizing ultralow oxygen smelting.
In a preferred embodiment of the invention, in the charging process, half of the Ni plate, all of the high purity graphite, all of the metallic Nb, half of the Co plate, and half of the pure Fe are added in sequence in the first batch, the rest of the Ni plate, the rest of the Co plate, and the rest of the pure Fe are added in the second batch, all of the single crystal Si and metallic Ti are added in sequence after the refining is completed, and all of the ferroboron and Ni-Mg alloy are added in sequence after argon is filled. And (3) charging in batches under vacuum after the material proportioning is finished, adding the materials along with the furnace materials in batches, wherein the first batch is sequentially added with 1/2Ni plate, all high-purity graphite, all metal Nb, 1/2Co plate and 1/2 pure Fe, the second batch is added with the rest 1/2Ni plate, 1/2Co plate and 1/2 pure Fe, all monocrystalline Si and metal Ti are sequentially added after the refining is finished, and all ferroboron and Ni-Mg alloy are sequentially added after Ar is filled. For low-carbon high-temperature alloy, the degassing effect of vacuum carbon-oxygen reaction is poor due to low carbon content, high-purity graphite is firstly fully mixed with a furnace during charging, the concentration of carbon content in alloy liquid in the melting process is improved, the degassing in the vacuum process is facilitated, and a reasonable charging sequence ensures that the follow-up smelting process realizes efficient degassing and nonmetallic inclusion removal. The raw material metal Nb with poor purity is added into a vacuum induction furnace along with the furnace, a molten pool formed after the first batch is melted is shallow, the ferrostatic pressure is small, gas is easier to remove, and the main alloying elements Ni plate, co plate and pure Fe are respectively added into one half of the batch, so that the vacuum carbon deoxidization effect in the melting process can be improved at a certain time in vacuum degree and temperature mainly by utilizing the elements such as Ni, co and the like.
In a preferred embodiment of the invention, in the melting process, three-stage pump vacuum pumping is adopted after the charging is completed, power transmission melting is started under the condition that the vacuum degree is less than or equal to 0.5Pa, the power transmission power of the first 30 mm is 300-500Kw, then the power transmission is carried out by adopting the power transmission power of 1300-1700Kw, the power transmission power is reduced to 800-1200Kw after an alloy liquid molten pool is formed, 100Kw power frequency stirring is adopted for 30min after the first raw material is melted, and 100Kw power frequency stirring is adopted for 30min after the second raw material is melted. After the charging is finished, three-stage pump vacuumizing is adopted, a higher vacuum degree is ensured in a melting period, power transmission melting is started under the condition that the vacuum degree is less than or equal to 0.5Pa, the front 30 mm controls the power transmission power to be 300-500Kw, and the small power transmission is used for protecting the crucible, then 1300-1700Kw of high power transmission is adopted until the raw materials at the bottom of the crucible are melted to form an alloy liquid melting pool, the main purpose is that the solid raw materials cannot be degassed, and the high power supply is adopted to be beneficial to shortening the smelting period. The power is reduced to 800-1200Kw after the molten alloy pool is formed and is melted slowly until all the furnace burden is completely melted. The furnace burden is slowly melted layer by layer from the surface to the inside under the high vacuum condition, so that the gas dissolved in the molten steel escapes from the molten steel and is removed outside the furnace, and on the other hand, the whole carbon content is added along with the furnace, so that carbon and oxygen can fully react, and generated carbon monoxide bubbles are removed under the vacuum condition, thereby being beneficial to removing the gas. After each batch of furnace burden is melted down, 100Kw of power frequency stirring is adopted for 30min, the stirring of molten steel is increased in the melting period, the static pressure of molten steel at the bottom of a large vacuum induction furnace molten pool is reduced, the dynamic condition of degassing is improved, the mass transfer coefficient of oxygen and nitrogen in the molten steel is increased, and the degassing speed is accelerated.
In a preferred embodiment of the invention, in the refining process, the vacuum degree in the refining period is controlled to be less than or equal to 0.1Pa, the power is transmitted and the temperature is increased to 1450-1470 ℃ for refining, and the refining time is 20-50min. After all furnace burden is melted and stirred at the power frequency, controlling the vacuum degree in the refining period to be less than or equal to 0.1Pa, transmitting power and heating to 1450-1470 ℃ for refining for 20-50min, and adopting high vacuum degree and low temperature for refiningThe smelting, the denitrification and the reduction of oxide inclusion in molten steel can be performed in a deep deoxidization and denitrification manner while reasonable refining time is controlled, and meanwhile, the decomposition and oxygen supply of the alkaline magnesia-alumina spinel refractory crucible can be prevented, and all Nb is added in the melting period, so that NbN is formed by the reaction of Nb and N, but the NbN can be decomposed and removed under the vacuum condition by controlling the vacuum degree and the refining temperature in the refining period (2NbN=2Nb+N according to the vacuum degree) 2 The decomposition temperature of the reaction nitride was found to be 1401℃under a vacuum of 0.1 Pa. After reasonable technological measures are adopted in the melting and refining processes, the oxygen and nitrogen content in the alloy is removed to a high-purity purification level that the oxygen content is less than or equal to 0.0010 percent and the nitrogen content is less than or equal to 0.0010 percent.
In a preferred embodiment of the invention, in the deoxidizing alloying process, the vacuum degree is controlled to be less than or equal to 0.1Pa, the residual gas content in the alloy liquid is removed by adding monocrystalline Si, then the alloying is carried out by adding metallic Ti, then the power is transmitted to be heated to 1450-1470 ℃, stirring and heat preservation are carried out for 30min, then 30000Pa of argon is filled, and then ferroboron and 0.02kg/t are added in sequence Alloy The Ni-Mg alloy of (C) was stirred for 5min. The vacuum degree is controlled to be less than or equal to 0.1Pa in the deoxidization alloying period, after refining, single crystal Si is added to further remove the residual gas content in the alloy liquid, then metal Ti is added to carry out alloying, then power is transmitted to and the temperature is raised to 1450-1470 ℃, stirring and heat preservation are carried out for 30min, 30000Pa Ar is filled, ferroboron is added firstly, and then 0.02kg/t is added Alloy And (3) carrying out final deoxidation on the Ni-Mg alloy, stirring for 5min, and tapping. The Ti pole activity ensures the oxygen and nitrogen content in molten steel before adding Ti, can avoid Ti and oxygen or nitrogen from forming a large amount of oxide and nitride inclusion, especially contains a large amount of Ti in alloy, and forms TiN inclusion to be decomposed only at 1943 ℃ under the condition of 0.1Pa of vacuum degree when the nitrogen content is higher, and can not be decomposed and removed under the condition of vacuum smelting; heating to 1450-1470 ℃, stirring and preserving heat for 30min, utilizing oxide inclusion generated by strong reductive deoxidization of carbon under high vacuum condition, filling 30000Pa Ar, stirring for 5min, and tapping to prevent volatilization of Ni-Mg alloy under vacuum condition, and improving yield and final deoxidization effect.
In a preferred embodiment of the invention, in the casting process, the steel is tapped with electricity at a casting temperature of 1450-1470 ℃.
In a preferred embodiment of the invention, the low carbon aluminum-free high niobium-iron-based superalloy is prepared in a 12 ton vacuum induction furnace. In other embodiments, other capacity vacuum induction furnaces may be used to produce low carbon aluminum free high niobium iron based superalloys.
The method of the invention has the advantages that: the problems of ultralow oxygen and nitrogen content smelting of a large vacuum induction furnace of the low-carbon aluminum-free high-niobium-iron-based superalloy are solved through reasonable matching of processes such as batching, charging, melting, refining, deoxidizing alloying and pouring, and the like, so that a high-purity vacuum induction ingot with oxygen content less than or equal to 0.0008% and nitrogen content less than or equal to 0.0008% is produced, the requirements of the harsh use environment of the low-carbon aluminum-free high-niobium-iron-based superalloy on purity are met, and the comprehensive performance and stability of the product are improved.
Example 1
This example is a 12 ton vacuum induction furnace for smelting GH2909 iron-based alloys using the method of the invention. The GH2909 comprises the following chemical components in percentage by mass: c is less than or equal to 0.03 percent, mn is less than or equal to 1 percent, si:0.25-0.5%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, cu is less than or equal to 0.5%, B is less than or equal to 0.012%, mo is less than or equal to 0.2%, al is less than or equal to 0.2%, cr is less than or equal to 1%, nb:4.3-5.2%, ti:1.3-1.80%, ni:35-40%, co:12-16%, fe balance.
Mainly comprises the following steps:
(1) and (3) batching: selecting high-purity graphite, single crystal Si, ferroboron, metal Nb, metal Ti, ni-Mg alloy, ni plate, co plate, pure Fe and other raw materials, carrying out surface treatment, then preparing materials according to the chemical component requirements of the low-carbon aluminum-free high-niobium-iron-based high-temperature alloy GH2909, analyzing, selecting and controlling the purity of oxygen, nitrogen and the like of various raw materials O total 0.02%、T N total 0.002% of high purity graphite is selected for carbon matching, and the carbon matching amount= (alloy target carbon content +3/4*T) O total ) 0.9, metal Ti is selected to replace sponge Ti to be matched with Ti, 0.02kg/t is added Alloy The Ni-Mg alloy is finally deoxidized.
(2) And (2) charging: and (3) charging in batches under vacuum after the material proportioning is finished, adding the materials along with the furnace materials in batches, wherein the first batch is sequentially added with 1/2Ni plate, all high-purity graphite, all metal Nb, 1/2Co plate and 1/2 pure Fe, the second batch is added with the rest 1/2Ni plate, 1/2Co plate and 1/2 pure Fe, all monocrystalline Si and metal Ti are sequentially added after the refining is finished, and all ferroboron and Ni-Mg alloy are sequentially added after Ar is filled.
(3) Melting: after the charging is completed, three-stage pump vacuumizing is adopted, power transmission and melting are started under the condition of the vacuum degree of 0.5Pa, the electric power of the first 30 mm is 500Kw, then high-power transmission of 1700Kw is adopted until the raw materials at the bottom of the crucible are melted to form an alloy liquid molten pool, after the alloy liquid molten pool is formed, the power is reduced to 800Kw and the alloy liquid molten pool is slowly melted until the alloy liquid molten pool is completely melted along with the furnace burden, the first batch of 1/2Ni plate, all high-purity graphite, all metal Nb, 1/2Co plate and 1/2 pure Fe are melted along with the furnace burden, then 100Kw power frequency stirring is adopted for 30min, then the second batch of the rest 1/2Ni plate, 1/2Co plate and 1/2 pure Fe along with the furnace burden are added under the vacuum condition, and the slow melting is continuously adopted for 800Kw power until the alloy liquid molten pool is completely melted along with the furnace burden, and 100Kw power frequency stirring is adopted for 30min.
(4) Refining: after all the furnace burden is melted and stirred at the power frequency, the vacuum degree in the refining stage is controlled to be 0.1Pa, the power is transmitted, the temperature is increased to 1470 ℃ for refining, and the refining time is 50min.
(5) Deoxidizing and alloying: sampling analysis, refining, namely adding monocrystalline Si for deoxidization after refining, adding metal Ti for alloying, then feeding power, heating to 1470 ℃, stirring and preserving heat for 30min, adding 30000Pa Ar, adding ferroboron, and then adding 0.02kg/t Alloy And (3) carrying out final deoxidation on the Ni-Mg alloy, stirring for 5min, and tapping.
(6) Casting: tapping with electricity, and casting at 1470 ℃.
The GH2909 low-carbon aluminum-free high-niobium-iron-based superalloy smelted in a 12-ton vacuum induction furnace by adopting the process samples a vacuum induction ingot to analyze oxygen and nitrogen, wherein the oxygen content in the vacuum induction ingot is 0.0007 percent and the nitrogen content in the vacuum induction ingot is 0.0008 percent, thereby meeting the requirement of the harsh use environment of the low-carbon aluminum-free high-niobium-iron-based superalloy on the purity and improving the comprehensive performance and stability of the product.
Example 2
This example is a 12 ton vacuum induction furnace for smelting GH2909 iron-based alloys using the method of the invention. The GH2909 comprises the following chemical components in percentage by mass: c is less than or equal to 0.03 percent, mn is less than or equal to 1 percent, si:0.25-0.5%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, cu is less than or equal to 0.5%, B is less than or equal to 0.012%, mo is less than or equal to 0.2%, al is less than or equal to 0.2%, cr is less than or equal to 1%, nb:4.3-5.2%, ti:1.3-1.80%, ni:35-40%, co:12-16%, fe balance.
Mainly comprises the following steps:
(1) and (3) batching: selecting high-purity graphite, single crystal Si, ferroboron, metal Nb, metal Ti, ni-Mg alloy, ni plate, co plate, pure Fe and other raw materials, carrying out surface treatment, then preparing materials according to the chemical component requirements of the low-carbon aluminum-free high-niobium-iron-based high-temperature alloy GH2909, analyzing, selecting and controlling the purity of oxygen, nitrogen and the like of various raw materials O total 0.015%、T N total 0.0018% of carbon is prepared by selecting high-purity graphite, and the carbon preparation amount= (alloy target carbon content +3/4*T) O total ) 0.9, metal Ti is selected to replace sponge Ti to be matched with Ti, 0.02kg/t is added Alloy The Ni-Mg alloy is finally deoxidized.
(2) And (2) charging: and (3) charging in batches under vacuum after the material proportioning is finished, adding the materials along with the furnace materials in batches, wherein the first batch is sequentially added with 1/2Ni plate, all high-purity graphite, all metal Nb, 1/2Co plate and 1/2 pure Fe, the second batch is added with the rest 1/2Ni plate, 1/2Co plate and 1/2 pure Fe, all monocrystalline Si and metal Ti are sequentially added after the refining is finished, and all ferroboron and Ni-Mg alloy are sequentially added after Ar is filled.
(3) Melting: after the charging is completed, three-stage pump vacuumizing is adopted, power transmission and melting are started under the condition of the vacuum degree of 0.3Pa, the electric power of the first 30 mm is 400Kw, then high-power transmission of 1500Kw is adopted until the raw materials at the bottom of the crucible are melted to form an alloy liquid molten pool, after the alloy liquid molten pool is formed, the power is reduced to 1000Kw, the alloy liquid molten pool is slowly melted until the alloy liquid molten pool is completely melted along with the furnace burden, the first batch of 1/2Ni plate, all high-purity graphite, all metal Nb, 1/2Co plate and 1/2 pure Fe are melted along with the furnace burden, then 100Kw power frequency stirring is adopted for 30min, then the rest 1/2Ni plate, 1/2Co plate and 1/2 pure Fe along with the furnace burden are added in the second batch under the vacuum condition, and the slow melting is continuously adopted for 1000Kw power until the alloy liquid molten pool is completely melted along with the furnace burden, and 100Kw power frequency stirring is adopted for 30min.
(4) Refining: after all the furnace burden is melted and stirred at the power frequency, the vacuum degree in the refining stage is controlled to be 0.08Pa, the power is transmitted, the temperature is raised to 1460 ℃ for refining, and the refining time is 30min.
(5) Deoxidizing and alloying: sampling analysis, analysis and refining, wherein the alloy gas content is 0.0008% and the nitrogen content is less than or equal to 0.0008%, the vacuum degree is controlled to be 0.07Pa, after refining, single crystal Si is firstly added for deoxidization, then metal Ti is added for alloying, then power is transmitted, the temperature is raised to 1460 ℃, stirring and heat preservation are carried out for 30min, 30000Pa Ar is filled, ferroboron is firstly added, and then 0.02kg/t is added Alloy And (3) carrying out final deoxidation on the Ni-Mg alloy, stirring for 5min, and tapping.
(6) Casting: and tapping with electricity, wherein the casting temperature is 1460 ℃.
Adopting the process to carry out oxygen and nitrogen analysis on vacuum induction ingot samples in GH2909 low-carbon aluminum-free high-niobium-iron-based superalloy smelted in a 12-ton vacuum induction furnace; the oxygen content in the vacuum induction ingot is 0.0006 percent, the nitrogen content is 0.0007 percent, the requirement of the harsh use environment of the low-carbon aluminum-free high-niobium-iron-based superalloy on the purity is met, and the comprehensive performance and stability of the product are improved.
Example 3
This example is a 12 ton vacuum induction furnace for smelting GH2909 iron-based alloys using the method of the invention. The GH2909 comprises the following chemical components in percentage by mass: c is less than or equal to 0.03 percent, mn is less than or equal to 1 percent, si:0.25-0.5%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, cu is less than or equal to 0.5%, B is less than or equal to 0.012%, mo is less than or equal to 0.2%, al is less than or equal to 0.2%, cr is less than or equal to 1%, nb:4.3-5.2%, ti:1.3-1.80%, ni:35-40%, co:12-16%, fe balance.
Mainly comprises the following steps:
(1) and (3) batching: selecting high-purity graphite, single crystal Si, ferroboron, metal Nb, metal Ti, ni-Mg alloy, ni plate, co plate, pure Fe and other raw materials, carrying out surface treatment, then preparing materials according to the chemical component requirements of the low-carbon aluminum-free high-niobium-iron-based high-temperature alloy GH2909, analyzing, selecting and controlling the purity of oxygen, nitrogen and the like of various raw materials O total 0.005%、T N total 0.0015% of carbon is prepared by selecting high-purity graphite, and the carbon preparation amount= (alloy target carbon content +3/4*T) O total ) 0.9, metal Ti is selected to replace sponge Ti to be matched with Ti, 0.02kg/t is added Alloy The Ni-Mg alloy is finally deoxidized.
(2) And (2) charging: and (3) charging in batches under vacuum after the material proportioning is finished, adding the materials along with the furnace materials in batches, wherein the first batch is sequentially added with 1/2Ni plate, all high-purity graphite, all metal Nb, 1/2Co plate and 1/2 pure Fe, the second batch is added with the rest 1/2Ni plate, 1/2Co plate and 1/2 pure Fe, all monocrystalline Si and metal Ti are sequentially added after the refining is finished, and all ferroboron and Ni-Mg alloy are sequentially added after Ar is filled.
(3) Melting: after the charging is completed, three-stage pump vacuumizing is adopted, power transmission and melting are started under the condition of the vacuum degree of 0.25Pa, the electric power of the first 30 mm is 300Kw, then high-power transmission of 1300Kw is adopted until the raw materials at the bottom of the crucible are melted to form an alloy liquid molten pool, after the alloy liquid molten pool is formed, the power is reduced to 1200Kw and is slowly melted until the alloy liquid molten pool is completely melted along with the furnace burden, the first batch of 1/2Ni plate, all high-purity graphite, all metal Nb, 1/2Co plate and 1/2 pure Fe are melted along with the furnace burden, then 100Kw power frequency stirring is adopted for 30min, then the rest 1/2Ni plate, 1/2Co plate and 1/2 pure Fe along with the furnace burden in the second batch are added under the vacuum condition, and the slow melting is continuously adopted until the alloy liquid molten pool is completely melted along with the furnace burden, and the 100Kw power frequency stirring is adopted for 30min.
(4) Refining: after all the furnace burden is melted and stirred at the power frequency, the vacuum degree in the refining period is controlled to be 0.05Pa, the power is transmitted, the temperature is increased to 1450 ℃ for refining, and the refining time is 20min.
(5) Deoxidizing and alloying: sampling analysis, refining, adding single crystal Si for deoxidization, adding metal Ti for alloying, feeding power, heating to 1450 ℃, stirring, preserving heat for 30min, adding 30000Pa Ar, adding ferroboron, and adding 0.02kg/t Alloy And (3) carrying out final deoxidation on the Ni-Mg alloy, stirring for 5min, and tapping.
(6) Casting: and tapping with electricity, wherein the casting temperature is 1450 ℃.
Adopting the process to carry out oxygen and nitrogen analysis on vacuum induction ingot samples in GH2909 low-carbon aluminum-free high-niobium-iron-based superalloy smelted in a 12-ton vacuum induction furnace; the oxygen content in the vacuum induction ingot is 0.0004 percent, the nitrogen content is 0.0005 percent, the requirements of the harsh use environment of the low-carbon aluminum-free high-niobium-iron-based superalloy on the purity are met, and the comprehensive performance and the stability of the product are improved.
In a second aspect of the embodiment of the invention, a low-carbon aluminum-free high-niobium-iron-based superalloy is provided, which is prepared by the method and comprises the following components in percentage by mass:
c is less than or equal to 0.03 percent, mn is less than or equal to 1 percent, si:0.25-0.5%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, cu is less than or equal to 0.5%, B is less than or equal to 0.012%, mo is less than or equal to 0.2%, cr is less than or equal to 1%, nb:4.3-5.2%, ti:1.3-1.80%, ni:35-40%, co:12-16%, and the balance of Fe and unavoidable impurities.
In a preferred embodiment of the present invention, the unavoidable impurities have an oxygen content of 0.0008% or less and a nitrogen content of 0.0008% or less, in mass%.
It should be noted that, each component or step in each embodiment may be intersected, replaced, added, deleted, and thus, the combination formed by these reasonable permutation and combination transformations shall also belong to the protection scope of the present invention, and shall not limit the protection scope of the present invention to the embodiments.
The foregoing is an exemplary embodiment of the present disclosure, and the order in which the embodiments of the present disclosure are disclosed is merely for the purpose of description and does not represent the advantages or disadvantages of the embodiments. It should be noted that the above discussion of any of the embodiments is merely exemplary and is not intended to suggest that the scope of the disclosure of embodiments of the invention (including the claims) is limited to these examples and that various changes and modifications may be made without departing from the scope of the invention as defined in the claims. The functions, steps and/or actions of the method claims in accordance with the disclosed embodiments described herein need not be performed in any particular order. Furthermore, although elements of the disclosed embodiments may be described or claimed in the singular, the plural is contemplated unless limitation to the singular is explicitly stated.
Those of ordinary skill in the art will appreciate that: the above discussion of any embodiment is merely exemplary and is not intended to imply that the scope of the disclosure of embodiments of the invention, including the claims, is limited to such examples; combinations of features of the above embodiments or in different embodiments are also possible within the idea of an embodiment of the invention, and many other variations of the different aspects of the embodiments of the invention as described above exist, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, equivalent substitutions, improvements, and the like, which are made within the spirit and principles of the embodiments of the invention, are included within the scope of the embodiments of the invention.

Claims (5)

1. The preparation method of the low-carbon aluminum-free high-niobium-iron-based superalloy is characterized by comprising the following steps of:
and (3) a batching procedure: selecting high-purity graphite, single crystal Si, ferroboron, metal Nb, metal Ti, ni-Mg alloy, ni plate, co plate and pure Fe, and mixing the raw materials according to the proportion of C less than or equal to 0.03%, mn less than or equal to 1%, si:0.25-0.5%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, cu is less than or equal to 0.5%, B is less than or equal to 0.012%, mo is less than or equal to 0.2%, cr is less than or equal to 1%, nb:4.3-5.2%, ti:1.3-1.80%, ni:35-40%, co:12-16%, and the balance of Fe is prepared by mass percent, and the total oxygen content brought into the raw materials is controlled to be less than or equal to 0.02%, and the nitrogen content is controlled to be less than or equal to 0.002%;
and (3) charging: charging raw materials according to two batches under a vacuum condition after the material proportioning is finished, sequentially adding half of Ni plates, all high-purity graphite, all metal Nb, half of Co plates and half of pure Fe into the first batch, and adding the rest of Ni plates, the rest of Co plates and the rest of pure Fe into the second batch;
and (3) a melting procedure: after the charging is finished, adopting a three-stage pump to vacuumize, starting to transmit power and melt under the condition that the vacuum degree is less than or equal to 0.5Pa, transmitting power of the first 30 mm is 300-500kW, transmitting power of 1300-1700kW, reducing the transmitted power to 800-1200kW after an alloy liquid molten pool is formed, stirring for 30min at 100kW power frequency after the first raw material is melted, and stirring for 30min at 100kW power frequency after the second raw material is melted;
refining: after stirring, controlling the vacuum degree in the refining period to be less than or equal to 0.1Pa, and transmitting power and heating to 1450-1470 ℃ for refining for 20-50min;
deoxidizing and alloying process: after refining, controlling the vacuum degree to be less than or equal to 0.1Pa, adding monocrystalline Si to remove the residual gas content in the alloy liquid, adding metal Ti to carry out alloying, then sending power to raise the temperature to 1450-1470 ℃, stirring and preserving heat for 30min, then charging 30000Pa of argon, and then sequentially adding ferroboron and 0.02kg/t Alloy Stirring the Ni-Mg alloy for 5min;
casting procedure: and tapping with electricity, wherein the casting temperature is a seventh preset value.
2. The method for preparing the low-carbon aluminum-free high-niobium-iron-based superalloy according to claim 1, wherein in the casting step, the steel is tapped with electricity, and the casting temperature is 1450-1470 ℃.
3. The method for preparing the low-carbon aluminum-free high-niobium-iron-based superalloy according to claim 1, wherein the low-carbon aluminum-free high-niobium-iron-based superalloy is prepared in a 12-ton vacuum induction furnace.
4. The low-carbon aluminum-free high-niobium-iron-based superalloy is characterized by being prepared by the preparation method of any one of claims 1 to 3, and comprising the following components in percentage by mass:
c is less than or equal to 0.03 percent, mn is less than or equal to 1 percent, si:0.25-0.5%, P is less than or equal to 0.015%, S is less than or equal to 0.015%, cu is less than or equal to 0.5%, B is less than or equal to 0.012%, mo is less than or equal to 0.2%, cr is less than or equal to 1%, nb:4.3-5.2%, ti:1.3-1.80%, ni:35-40%, co:12-16%, and the balance of Fe and unavoidable impurities.
5. The low-carbon aluminum-free high-niobium-iron-based superalloy as claimed in claim 4, wherein the unavoidable impurities have an oxygen content of 0.0008% or less and a nitrogen content of 0.0008% or less in mass percent.
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