CN113584381B - High-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy and electroslag remelting method thereof - Google Patents
High-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy and electroslag remelting method thereof Download PDFInfo
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Abstract
The invention relates to the field of metallurgy, in particular to a high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy and an electroslag remelting method thereof, wherein when the environment temperature of the prepared high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy is-60 ℃, the low-temperature impact power is more than or equal to 61J, the room-temperature tensile strength is more than or equal to 1030Mpa, the yield strength is more than or equal to 860Mpa, the elongation is more than or equal to 19%, the reduction of area is more than or equal to 25%, the Rockwell hardness is 30-40 HRC, the grain size is more than or equal to 2.5 grade, the structure is uniform and compact, sigma phases, LAVES and other topologically closely-arranged brittle phases cannot be separated out in the structure, the later-stage thermal deformation is facilitated, cracks are not easy to generate in the thermal processing process of the alloy, the yield of the alloy in the thermal processing process is greatly improved, especially for large-size bar products with the diameter of more than 300mm, the segregation degree of chemical components of an electroslag ingot is well controlled, and the forging performance is excellent.
Description
Technical Field
The invention relates to the field of metallurgy, in particular to a high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy and an electroslag remelting method thereof.
Background
Nickel-based alloys such as MonelK-500, inconel690 and UNS718 are the mainstream manufacturing materials of equipment and components which are currently applied to various corrosive environments.
The nickel-based alloy is excellent in performance, but the manufacturing cost is greatly influenced by the market price of the raw material nickel because of its high nickel content. Particularly, since 2020, the price of raw materials fluctuates sharply, and the rising amplitude of nickel price in 2021 reaches more than 30%, which has a great impact on the cost control of alloy production enterprises. In order to control the manufacturing cost of the nickel-based alloy with excellent performance and improve the market risk resistance of enterprises, some special alloy manufacturing enterprises in developed countries such as: baker Hughes, special Metals and other companies have developed corrosion-resistant alloys with low nickel content for various corrosion environments such as petroleum, the manufacturing cost of the nickel-based alloy is greatly reduced by adding cheaper alloy elements to replace part of nickel, and the mechanical property of the nickel-based alloy manufactured according to the method can be similar to that of UNS718, so that the nickel-based alloy has considerable market application prospect.
The high-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy is originally designed to have low nickel content (namely, the nickel content is 46-49%), but needs to keep good material mechanical properties, and has good corrosion resistance and mechanical properties only through reasonable collocation of alloy elements such as Nb, cr, mo, cu and the like. Meanwhile, because the content of nickel in the alloy is low, the forging interval in a hot working area is very narrow, and in order to improve the hot working performance of the alloy and ensure the actual producibility of the alloy, a small amount of microalloy elements are required to be added to improve the hot working performance of the alloy. After forging, solid solution and aging treatment, the alloy can obtain excellent comprehensive mechanical properties close to the performance of UNS718 alloy.
The standard compositions of the commonly used corrosion resistant alloys UNS718 and Inconel690 are shown in Table 1, where the mechanical properties tensile strength R of UNS718 m The lowest is 820MPa, and the highest can reach about 1400 MPa; and Inconel690 alloy has the lowest tensile strength R m Not less than 580MPa, and the highest can reach 700MPa.
TABLE 1
At present, the research on the replacement of traditional UNS718, inconel690 and MonelK-500 materials by the high-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy is a new guide for the energy and petroleum industry market.
However, because a large amount of Nb and Cu are added to the high-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy, and Nb and Cu are strong segregation elements in the electroslag remelting process, macro segregation is easily caused, and cracking is caused in the later hot working process. The factors are not beneficial to later-stage thermal deformation, cracks are easy to generate in the later-stage hot processing process, the yield in the hot processing process is seriously reduced, particularly for large-size bar products with the diameter larger than 300mm, if the chemical composition segregation degree of an electroslag ingot cannot be controlled by an electroslag process, the generated macrosegregation cannot be obviously improved by subsequent diffusion annealing and other processes, and the forging performance is poor.
Disclosure of Invention
The invention aims to provide a high-strength copper-containing Ni-Fe-Cr-based age hardening corrosion-resistant alloy and an electroslag remelting method thereof aiming at the corresponding defects of the prior art, the prepared alloy has uniform and compact structure, cannot precipitate sigma phase, LAVES and other topologically close brittle phases in the structure, is beneficial to later-stage thermal deformation, is not easy to generate cracks in the hot processing process of the alloy, greatly improves the yield of the alloy in the hot processing process, and particularly aims at large-size bar products with the diameter of more than 300mm, the chemical composition segregation degree of an electroslag ingot is well controlled, and the forging performance is excellent.
The purpose of the invention is realized by adopting the following scheme: a high-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy comprises the following components in percentage by weight: less than or equal to 0.03 percent of C, less than or equal to 0.3 percent of Si, less than or equal to 0.5 percent of Mn, less than or equal to 23 percent of Cr more than or equal to 18 percent, less than or equal to 49 percent of Ni more than or equal to 46 percent, less than or equal to 4 percent of Mo more than or equal to 2.8 percent, less than or equal to 4 percent of Nb more than or equal to 2.8 percent, less than or equal to 3 percent of Cu more than or equal to 1.5 percent, less than or equal to 3 percent of Ti more than or equal to 1 percent, less than or equal to 0.5 percent of Al more than or equal to 0.15 percent, less than or equal to 0.005 percent of B, less than or equal to 0.15 percent of Zr, and the balance of Fe.
Preferably, the alloy comprises the following components in percentage by weight: c is more than or equal to 0.012 percent and less than or equal to 0.023 percent, si is more than or equal to 0.232 percent and less than or equal to 0.182 percent, mn is more than or equal to 0.496 percent and less than or equal to 0.472 percent, cr is more than or equal to 21.98 percent and less than or equal to 21.71 percent, ni is more than or equal to 48.46 percent and less than or equal to 47.11 percent and less than or equal to 3.75 percent of Mo, nb is more than or equal to 3.06 percent and less than or equal to 3.97 percent, cu is more than or equal to 1.88 percent and less than or equal to 2.06 percent, ti is more than or equal to 1.62 percent and less than or equal to 1.98 percent, al is more than or equal to 0.424 percent and less than or equal to 0.0041 percent and less than or equal to 0.0036 percent and less than or equal to 0.0041 percent, zr is more than or equal to 0.0107 and less than or equal to 0.15 percent, and the balance of Fe.
The high-strength copper-containing Ni-Fe-Cr-based age hardening corrosion-resistant alloy comprises the following components in percentage by mass: c + Si + Mn is less than 1 percent.
An electroslag remelting method for high-strength copper-containing Ni-Fe-Cr-based age hardening corrosion resistant alloy comprises the following steps:
1) Vacuum melting and casting the alloy raw material into a round bar, and finishing to obtain a remelting electrode bar for high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy electroslag remelting;
the round bar first needs surface sanding to remove the scale and then is finished.
The alloy comprises the following raw materials in percentage by weight: less than or equal to 0.03 percent of C, less than or equal to 0.3 percent of Si, less than or equal to 0.6 percent of Mn, less than or equal to 22 percent of Cr which is more than or equal to 17 percent, less than or equal to 49 percent of Ni which is more than or equal to 46 percent, less than or equal to 5 percent of Mo which is more than or equal to 2.8 percent, less than or equal to 5 percent of Nb which is more than or equal to 2.8 percent, less than or equal to 3 percent of Cu which is more than or equal to 1.5 percent, less than or equal to 3 percent of Ti which is more than or equal to 0.5 percent, less than or equal to 0.7 percent of Al which is more than or equal to 0.15 percent, less than or equal to 0.005 percent of B, less than or equal to 0.2 percent of Zr, and the balance of Fe;
preferably, the alloy raw materials comprise the following components in percentage by weight: less than or equal to 0.03 percent of C, less than or equal to 0.3 percent of Si, less than or equal to 0.46 percent of Mn, less than or equal to 23 percent of Cr which is more than or equal to 18 percent, less than or equal to 49 percent of Ni which is more than or equal to 47 percent, less than or equal to 4 percent of Mo which is more than or equal to 3 percent, less than or equal to 4 percent of Nb which is more than or equal to 3 percent, less than or equal to 3 percent of Cu which is more than or equal to 1.5 percent, less than or equal to 3 percent of Ti which is more than or equal to 1 percent, less than or equal to 0.5 percent of Al which is more than or equal to 0.3 percent, less than or equal to 0.005 percent of B, less than or equal to 0.15 percent of Zr which is more than or equal to 0.05 percent, and the balance of Fe.
The remelting electrode rod contains less than or equal to 0.004 percent of boron and less than or equal to 0.12 percent of zirconium.
2) Taking the components of the slag, fully and uniformly mixing, baking at 800 ℃ for not less than 3h, and carrying out arc starting and slag melting;
the slag comprises the following components in parts by weight: caF 2 : 65-75 parts; caO: 8-15 parts; al (aluminum) 2 O 3 : 10-18 parts; mgO: 5-11 parts;
preferably, the components of the slag system are CaF in parts by weight 2 : 65-75 parts; caO: 10-12 parts; al (Al) 2 O 3 : 10-18 parts; mgO:5 to 7 portions.
Slowly inserting a remelting electrode rod into a slag pool in a molten state, adjusting voltage and current according to the diameter of the remelting electrode rod after electrifying and arcing, and melting materials;
when the diameter of the remelting electrode bar is 80-150 mm, the current is (3-4) +/-0.5 kA, and the voltage is (40-45) +/-5V; when the diameter is 151-400 mm, the current is (7-14) + -0.5 kA, the voltage is (45-60) + -2V, namely the current and the voltage values in the remelting process are adjusted according to the diameter of the remelting electrode rod.
The slag of electroslag remelting is uniformly mixed, heated to a temperature not lower than 800 ℃ in a box-type resistance furnace, dried for not less than 3 hours, and electrified and arc-started in a cast iron crucible or a crystallizer by using a graphite electrode bar and heated to a molten state.
And the increment of harmful elements such as P, S is controlled by basic oxides such as CaO and MgO in the slag, so that the content of P in the obtained electroslag ingot is not more than 30ppm, and the content of S is not more than 15ppm.
3) Cooling and demoulding after remelting to obtain an electroslag ingot;
the content of P in the electroslag ingot is not more than 30ppm, and the content of S is not more than 15ppm.
Usually, before remelting, hot-feeding is carried out to obtain an electroslag ingot, the electroslag ingot is placed in a crystallizer for cooling and then demoulding, and the cooling time is more than or equal to 30min.
And the thermal feeding adopts a power successive subtraction method, and the feeding initial current is electroslag remelting finishing current.
4) The electroslag ingot is forged into a bar after hot working, and the high-strength copper-containing Ni-Fe-Cr-based age hardening corrosion resistant alloy is obtained after solid solution and aging treatment.
The high-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy has the advantages that when the ambient temperature is-60 ℃, the low-temperature impact energy is more than or equal to 61J, the room-temperature tensile strength is more than or equal to 1030Mpa, the yield strength is more than or equal to 860Mpa, the elongation is more than or equal to 19%, the reduction of area is more than or equal to 25%, the Rockwell hardness is 30-40 HRC, and the grain size is more than or equal to 2.5 grade.
The invention has the following beneficial effects: the Ni, cr and Fe elements in the high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy are basic elements of the nickel-based alloy, so that the nickel-based corrosion-resistant alloy has an austenite matrix and corrosion resistance.
At present, the Ni content in a high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy system is usually 53 percent, the Ni content in the high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy prepared by the invention is more than or equal to 46 percent and less than or equal to 49 percent, the Ni content is less than 53 percent, and Cu and Nb are adopted to replace partial nickel to ensure the mechanical property and the corrosion resistance of the alloy. However, excessive Cu can reduce the thermoplasticity of the alloy and affect the hot-working performance, so when the corrosion-resistant alloy is prepared by the method, the Cu content in the alloy raw materials is limited to be within the range of 1.5 percent to 3 percent, so that the problems are avoided.
Nb, ti and Al are main components of reinforced precipitation phases gamma 'and gamma' of the precipitation type hard alloy, the hot working performance is reduced due to excessive addition, and the performance is insufficient due to too low addition.
Ti and Al are elements easy to segregate and burn, and because excessive Ti and Al are added in the electroslag remelting smelting process, the prepared electroslag ingot has serious component segregation and is not beneficial to later thermal processing treatment and material performance stabilization, when the corrosion-resistant alloy is prepared, the content of Ti in the alloy raw materials is more than or equal to 0.5% and less than or equal to 3%, and the content of Al is more than or equal to 0.15% and less than or equal to 0.7%.
Mo and Nb are solid solution strengthening elements of the nickel-based alloy. Mo being M 6 The main chemical combination elements of C are excessive and easily form a grain boundary carbide coating film, a topological close-packed phase is formed, the toughness of the alloy is reduced, and the content of the C needs to be properly controlled, so that when the corrosion-resistant alloy is prepared, the Mo content in the alloy raw material is more than or equal to 2.8% and less than or equal to 5%.
C. Si and Mn elements can deoxidize and refine the alloy, improve the fluidity of liquid metal and improve the casting performance of the metal, but the elements are easy to form a TCP phase such as LAVES and segregate grain boundaries, so that the strength of the grain boundaries of the alloy is reduced, and the weight percentages of the three elements in the alloy meet the following conditions:
w(C)+w(Si)+w(Mn)＜1％
wherein w (C) is the weight percentage of C in the prepared alloy, w (Si) is the weight percentage of Si in the prepared alloy, and w (Mn) is the weight percentage of Mn in the prepared alloy.
The content of boron in the remelting electrode rod is less than or equal to 0.004 percent, the content of an alloy element boron in the nickel-based corrosion-resistant alloy is dozens of ppm, excessive boron causes segregation of crystal boundary, the heat strength of the material is influenced, and cracking along the crystal boundary is easily caused in the forging process.
The content of zirconium in the remelting electrode bar is less than or equal to 0.12 percent, the zirconium improves the carbide form of the alloy, improves the hot cracking tendency of the alloy, and the excessive zirconium influences the toughness of the alloy.
When the high-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy with the nickel content of between 46 and 49 percent is prepared, if the slag material is not adopted, the flaw detection is unqualified after forging, the internal cracks are generated, the metallographic phase shows that a large amount of looseness exists, and the Nb-rich phase is obviously more; if the slag material is adopted, electroslag remelting production is carried out, flaw detection is qualified after forging, the metallographic phase shows that the structure is uniform, harmful phases do not exist, and the yield is high.
The applicant verifies through experiments that when the environment temperature is-60 ℃, the low-temperature impact energy of the high-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy is more than or equal to 61J, the room-temperature tensile strength is more than or equal to 1030Mpa, the yield strength is more than or equal to 860Mpa, the elongation is more than or equal to 19%, the reduction of area is more than or equal to 25%, the Rockwell hardness is 30-40 HRC, and the grain size is more than or equal to 2.5 grade.
The high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy is suitable for the application of chemical industry, ocean industry and energy industry which have requirements on economic cost, material strength, high temperature and corrosion resistanceIs especially suitable for preparing a material simultaneously containing high CO 2 、H 2 S, cl-and elemental S-bearing member for deep sea oil and gas environment exploitation.
Drawings
FIG. 1 is a gold phase diagram of an alloy prepared in example 1 of the present invention;
fig. 2 is a metallographic structure diagram of an alloy prepared using other electroslag slag.
Detailed Description
As shown in figures 1 to 2, the high-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy comprises the following components in percentage by weight: less than or equal to 0.03 percent of C, less than or equal to 0.3 percent of Si, less than or equal to 0.5 percent of Mn, more than or equal to 18 percent and less than or equal to 23 percent of Cr, more than or equal to 46 percent and less than or equal to 49 percent of Ni, more than or equal to 2.8 percent and less than or equal to 4 percent of Mo, more than or equal to 2.8 percent and less than or equal to 4 percent of Nb, more than or equal to 1.5 percent and less than or equal to 3 percent of Cu, more than or equal to 1 percent and less than or equal to 3 percent of Ti, more than or equal to 0.15 percent and less than or equal to 0.5 percent of Al, less than or equal to 0.005 percent of B, less than or equal to 0.15 percent of Zr, and the balance of Fe.
Preferably, the alloy comprises the following components in percentage by weight: c is more than or equal to 0.012 percent and less than or equal to 0.023 percent, si is more than or equal to 0.182 percent and less than or equal to 0.232 percent, mn is more than or equal to 0.472 percent and less than or equal to 0.496 percent, cr is more than or equal to 21.71 percent and less than or equal to 21.98 percent, ni is more than or equal to 47.11 percent and less than or equal to 48.46 percent, mo is more than or equal to 3.41 percent and less than or equal to 3.75 percent, nb is more than or equal to 3.06 percent and less than or equal to 3.97 percent, cu is more than or equal to 1.88 percent and less than or equal to 2.06 percent, ti is more than or equal to 1.98 percent and less than or equal to 1.208 percent and less than or equal to 0.424 percent, B is more than or equal to 0.0041 percent and less than or equal to 0.0036 percent, zr is more than or equal to 0.15 percent and less than or equal to 0.0107 percent, and the balance is Fe.
The high-strength copper-containing Ni-Fe-Cr-based age hardening corrosion-resistant alloy comprises the following components in percentage by mass: c + Si + Mn is less than 1%, namely the weight percentages of the three elements of C, si and Mn in the alloy meet the following conditions:
w(C)+w(Si)+w(Mn)＜1％
wherein w (C) is the weight percent of C in the prepared alloy, w (Si) is the weight percent of Si in the prepared alloy, and w (Mn) is the weight percent of Mn in the prepared alloy.
The electroslag remelting method for preparing the high-strength copper-containing Ni-Fe-Cr-based age hardening corrosion-resistant alloy comprises the following steps:
1) Vacuum melting and casting the alloy raw material into a round bar, and finishing to obtain a remelting electrode bar for high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy electroslag remelting;
the round bar is firstly subjected to surface sanding, and then is subjected to finishing after oxide scales are removed.
The alloy comprises the following raw materials in percentage by weight: less than or equal to 0.03 percent of C, less than or equal to 0.3 percent of Si, less than or equal to 0.6 percent of Mn, less than or equal to 22 percent of Cr which is more than or equal to 17 percent, less than or equal to 49 percent of Ni which is more than or equal to 46 percent, less than or equal to 5 percent of Mo which is more than or equal to 2.8 percent, less than or equal to 5 percent of Nb which is more than or equal to 2.8 percent, less than or equal to 3 percent of Cu which is more than or equal to 1.5 percent, less than or equal to 3 percent of Ti which is more than or equal to 0.5 percent, less than or equal to 0.7 percent of Al which is more than or equal to 0.15 percent, less than or equal to 0.005 percent of B, less than or equal to 0.2 percent of Zr, and the balance of Fe;
preferably, the alloy raw materials comprise the following components in percentage by weight: less than or equal to 0.03 percent of C, less than or equal to 0.3 percent of Si, less than or equal to 0.46 percent of Mn, less than or equal to 23 percent of Cr which is more than or equal to 18 percent, less than or equal to 49 percent of Ni which is more than or equal to 47 percent, less than or equal to 4 percent of Mo which is more than or equal to 3 percent, less than or equal to 4 percent of Nb which is more than or equal to 3 percent, less than or equal to 3 percent of Cu which is more than or equal to 1.5 percent, less than or equal to 3 percent of Ti which is more than or equal to 1 percent, less than or equal to 0.5 percent of Al which is more than or equal to 0.3 percent, less than or equal to 0.005 percent of B, less than or equal to 0.15 percent of Zr which is more than or equal to 0.05 percent, and the balance of Fe.
The content of boron in the remelting electrode rod is less than or equal to 0.004 percent, and the content of zirconium is less than or equal to 0.12 percent.
2) Taking the components of the slag, fully and uniformly mixing, baking at 800 ℃ for not less than 3h, and carrying out arc starting and slag melting;
the slag comprises the following components in parts by weight: caF 2 : 65-75 parts; caO: 8-15 parts; al (Al) 2 O 3 : 10-18 parts; mgO: 5-11 parts;
preferably, the components of the slag system are CaF in parts by weight 2 : 65-75 parts; caO: 10-12 parts; al (aluminum) 2 O 3 : 10-18 parts; mgO:5 to 7 portions.
Slowly inserting a remelting electrode rod into a slag pool in a molten state, adjusting voltage and current according to the diameter of the remelting electrode rod after electrifying and arcing, and melting materials;
when the diameter of the remelting electrode bar is 80-150 mm, the current is (3-4) +/-0.5 kA, and the voltage is (40-45) +/-5V; when the diameter is 151-400 mm, the current is (7-14) + -0.5 kA, the voltage is (45-60) + -2V, namely the current and the voltage values in the remelting process are adjusted according to the diameter of the remelting electrode rod.
The slag of electroslag remelting is uniformly mixed, heated to a temperature not lower than 800 ℃ in a box-type resistance furnace, dried for not less than 3 hours, and electrified and arc-started in a cast iron crucible or a crystallizer by using a graphite electrode bar and heated to a molten state.
And the increment of harmful elements such as P, S is controlled by basic oxides such as CaO and MgO in the slag, so that the content of P in the obtained electroslag ingot is not more than 30ppm, and the content of S is not more than 15ppm.
3) Cooling and demoulding after remelting to obtain an electroslag ingot;
the content of P in the electroslag ingot is not more than 30ppm, and the content of S is not more than 15ppm.
Usually, before remelting, hot-feeding is carried out to obtain an electroslag ingot, the electroslag ingot is placed in a crystallizer for cooling and then demoulding, and the cooling time is more than or equal to 30min.
The thermal feeding adopts a power decreasing method, and feeding initial current is electroslag remelting finishing current.
4) The electroslag ingot is forged into a bar after hot working, and the high-strength copper-containing Ni-Fe-Cr-based age hardening corrosion resistant alloy is obtained after solid solution and aging treatment.
The high-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy has the advantages that when the ambient temperature is-60 ℃, the low-temperature impact energy is more than or equal to 61J, the room-temperature tensile strength is more than or equal to 1030Mpa, the yield strength is more than or equal to 860Mpa, the elongation is more than or equal to 19%, the reduction of area is more than or equal to 25%, the Rockwell hardness is 30-40 HRC, and the grain size is more than or equal to 2.5 grade.
The following examples were made according to the above method to prepare high strength copper-containing Ni-Fe-Cr based age-hardenable corrosion resistant alloys of different properties:
example 1
a) Preparation of remelted electrode bar
According to the total weight of 60kg of alloy in each furnace, the remelting electrode bar for preparing the high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy comprises the following components in percentage by weight: 48% of Ni, 22% of Cr, 2% of Ti, 0.5% of Al, 4% of Mo, 2% of Cu, 0.4% of Mn, 0.2% of Si, 3.6% of Nb, 0.02% of C, 0.004% of B, 0.01% of Zr and the balance of Fe, casting into a round rod with phi 100mm through vacuum induction melting, and sanding and finishing the surface of the round rod to obtain the remelting electrode rod used in electroslag remelting, wherein the length of the remelting electrode rod is 95mm.
b) Electroslag remelting
(1) The slag charge is calculated according to the usage of 5kg in each furnace, and the slag charge comprises the following components in parts by weight: caF 2 Is 65 portions of Al 2 O 3 18 parts of CaO, 10 parts of CaO and 7 parts of MgO, uniformly mixing, drying at 800 ℃ for 3 hours, and heating the slag in a cast iron crucible to a molten state through a graphite electrode rod.
(2) Slowly lowering the prepared remelting electrode rod into molten electroslag remelting slag, adjusting remelting voltage to 45V +/-5V and gradually adjusting current to (3-4) +/-0.5 kA after electrifying and arcing;
(3) the remelting electrode rod is slowly melted by resistance heat, liquid drops of the remelting electrode rod pass through a melted slag layer to perform chemical reaction with slag to obtain purified liquid drops, and the liquid drops are recrystallized at the bottom of the crystallizer to obtain an electroslag ingot with the phi of 160 mm.
The detection shows that the harmful elements S in the electroslag ingot are less than 11ppm, P is less than 12ppm, and the contents of P and S are qualified.
c) Alloy Performance testing
The electroslag ingot is forged into a bar through hot working, and after solid solution and aging treatment, the high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion resistant alloy comprises the following components in percentage by weight: 0.023% of C, 0.232% of Si, 0.472% of Mn, 21.98% of Cr, 48.46% of Ni, 3.75% of Mo, 3.97% of Nb, 2.06% of Cu, 1.98% of Ti, 0.424% of Al, 0.0041% of B, 0.0107% of Zr and the balance of Fe; when the environment temperature is-60 ℃, the low-temperature impact energy is 64J, the room-temperature tensile strength is 1368MPa, the yield strength is 926MPa, the elongation is 26.5%, the reduction of area is 28%, and the Rockwell hardness is as follows: 38HRC, grain size grade 4.
Example 2
a) Preparation of remelted electrode rod
Calculated according to the total weight of 450kg of alloy in each furnace, the remelting electrode bar for preparing the high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy comprises the following components in percentage by weight: 47% of Ni, 22% of Cr, 1.5% of Ti, 0.3% of Al, 3.2% of Mo, 1.5% of Cu, 0.3% of Mn, 0.15% of Si, 3% of Nb, 0.015% of C, 0.003% of B, 0.15% of Zr and the balance of Fe, casting into a round rod with phi 260mm through vacuum induction melting, and sanding and finishing the surface of the round rod to obtain the remelting electrode rod used in electroslag remelting, wherein the length of the remelting electrode rod is 1800mm.
b) Electroslag remelting
(1) The slag charge is calculated according to the usage of 25kg in each furnace, and the slag charge comprises the following components in parts by weight: caF 2 75 portions of Al 2 O 3 10 parts of CaO, 10 parts of CaO and 5 parts of MgO, uniformly mixing the slag re-melted by the electroslag, heating the mixture in a box-type resistance furnace to be not less than 800 ℃, drying the mixture for not less than 3 hours, electrifying and arcing a graphite electrode bar in a crystallizer, heating the mixture to a molten state, and cooling the crystallizer and a bottom plate by water.
(2) Slowly lowering the prepared remelting electrode rod into molten electroslag remelting slag, and adjusting remelting voltage to 53V +/-2V and current to (7-14) +/-0.5 kA after electrifying and arcing;
(3) the remelting electrode bar is slowly melted by resistance heat, liquid drops of the remelting electrode bar penetrate through the melted slag layer to react with slag to obtain purified liquid, and the liquid drops are recrystallized at the bottom of the crystallizer to obtain an electroslag ingot with the diameter of phi 320 mm. Tests show that the prepared alloy contains the following harmful elements of sulfur and phosphorus: s =10ppm, p =18ppm; the contents of sulfur and phosphorus are qualified.
c) Alloy Performance testing
After the electroslag ingot is subjected to high-temperature homogenization diffusion annealing heat treatment, the electroslag ingot is heated and forged into a bar, and after solid solution and aging treatment, the high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion resistant alloy comprises the following components in percentage by weight: 0.012% of C, 0.182% of Si, 0.496% of Mn, 21.71% of Cr, 47.11% of Ni, 3.41% of Mo, 3.06% of Nb, 1.88% of Cu, 1.62% of Ti, 0.208% of Al, 0.0036% of B, 0.15% of Zr and the balance of Fe; when the environment temperature is-60 ℃, the low-temperature impact energy is 89J, the room-temperature tensile strength is 1135MPa, the yield strength is 885MPa, the elongation is 28.5%, the reduction of area is 44%, and the Rockwell hardness is as follows: 38.5HRC, grain size 4.5 grade.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and modifications of the present invention by those skilled in the art are within the scope of the present invention without departing from the spirit of the present invention.
Claims (7)
1. The high-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy is characterized by comprising the following components in percentage by weight: c is more than or equal to 0.012 percent and less than or equal to 0.023 percent, si is more than or equal to 0.232 percent and less than or equal to 0.182 percent, mn is more than or equal to 0.496 percent and less than or equal to 0.472 percent, cr is more than or equal to 21.98 percent and less than or equal to 21.71 percent, ni is more than or equal to 48.46 percent and less than or equal to 47.11 percent and less than or equal to 3.75 percent of Mo, nb is more than or equal to 3.06 percent and less than or equal to 3.97 percent, cu is more than or equal to 1.88 percent and less than or equal to 2.06 percent, ti is more than or equal to 1.62 percent and less than or equal to 1.98 percent, al is more than or equal to 0.424 percent and less than or equal to 0.0041 percent and less than or equal to 0.0036 percent and less than or equal to 0.0041 percent, zr is more than or equal to 0.0107 and less than or equal to 0.15 percent, and the balance of Fe.
2. A process for electroslag remelting of an alloy according to claim 1, comprising the steps of:
1) Vacuum melting and casting the alloy raw material into a round bar, and finishing to obtain a remelting electrode bar for high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion-resistant alloy electroslag remelting;
2) Taking all components of the slag, fully and uniformly mixing, baking at 800 ℃ for not less than 3h, and arcing to melt slag;
inserting a remelting electrode rod into a slag pool, adjusting voltage and current according to the diameter of the remelting electrode rod after electrifying and arcing, and melting;
3) Cooling and demoulding after remelting to obtain an electroslag ingot;
4) The electroslag ingot is forged into a bar after hot working, and the high-strength copper-containing Ni-Fe-Cr-based age hardening type corrosion resistant alloy is obtained after solid solution and aging treatment.
3. The method of claim 2, wherein: the slag comprises the following components in parts by weight: caF 2 : 65-75 parts; caO: 8-15 parts; al (Al) 2 O 3 : 10-18 parts; mgO:5 to 11 portions.
4. The method of claim 3, wherein: the slag comprises the following components in parts by weight: caF 2 : 65-75 parts; caO: 10-12 parts; al (Al) 2 O 3 : 10-18 parts; mgO:5 to 7 portions.
5. The method of claim 2, wherein: the content of P in the electroslag ingot is not more than 30ppm, and the content of S is not more than 15ppm.
6. The method of claim 2, wherein: when the diameter of the remelting electrode rod in the step 2) is 80-150 mm, the current is (3-4) +/-0.5 kA, and the voltage is (40-45) +/-5V; when the diameter is 151-400 mm, the current is (7-14) + -0.5 kA, and the voltage is (45-60) + -2V.
7. The method of claim 2, wherein: when the environmental temperature is-60 ℃, the low-temperature impact energy of the high-strength copper-containing Ni-Fe-Cr-based age-hardening corrosion-resistant alloy is not less than 61J, the room-temperature tensile strength is not less than 1030MPa, the yield strength is not less than 860MPa, the elongation is not less than 19%, the reduction of area is not less than 25%, the Rockwell hardness is 30-40 HRC, and the grain size is not less than 2.5 grade.
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