CN109136652B - Nickel-based alloy large-section bar for nuclear power key equipment and manufacturing method thereof - Google Patents
Nickel-based alloy large-section bar for nuclear power key equipment and manufacturing method thereof Download PDFInfo
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- CN109136652B CN109136652B CN201710450503.2A CN201710450503A CN109136652B CN 109136652 B CN109136652 B CN 109136652B CN 201710450503 A CN201710450503 A CN 201710450503A CN 109136652 B CN109136652 B CN 109136652B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
Abstract
The invention provides a nickel-based alloy for nuclear power key equipment and a preparation method of a bar thereof, wherein the alloy comprises the following elements: C. cr, Fe, W and V, and the balance of Ni and inevitable impurities, wherein the content of Ni is not less than 58%. The preparation method of the bar comprises the following steps: preparing nickel-based alloy, hot rolling and forming the bar and carrying out heat treatment on the bar. Compared with the prior art, the invention has the following beneficial effects: the manufacturing process is particularly suitable for manufacturing the nickel-based alloy bar with the large cross section of phi 300 mm-phi 660mm, is completely suitable for key parts of nuclear island equipment of a nuclear power station, and has important significance for effectively promoting the autonomous construction of large nuclear power stations in China.
Description
Technical Field
The invention relates to the technical field related to the manufacturing of nickel-based corrosion-resistant alloy bars, in particular to a component and a manufacturing method of a nickel-based alloy bar with an oversized cross section and special performance requirements. The method specifically comprises the key process technologies of components, smelting method, forging and heat treatment of the large-section nickel-based alloy bar.
Background
Nuclear power is advanced clean energy, is an important component of the national energy strategy, and is one of the most important measures for realizing the national energy-saving and emission-reducing targets. The general design life of nuclear power equipment is 60 years, and as the nickel-based alloy has excellent high temperature resistance and corrosion resistance, a large number of key components in the nuclear island are made of the nickel-based alloy, such as a steam generator lower end socket clapboard, a U-shaped heat exchange tube, a safety injection box, a reactor core water replenishing box, a pressure vessel, a control rod driving mechanism, a reactor internals, a pressure stabilizer, a blasting valve, a main pump flywheel cover plate, a main pump shielding sleeve, a heat exchanger, a pressure stabilizer and other equipment all have nickel-based alloy parts. The parts have special service environment, the integrity of the parts is directly used for stable operation of the nuclear power station, and the parts have high requirements on mechanical property, corrosion resistance and the like, wherein the nickel-based alloy for the shearing cover of the blasting valve is the most severe. The blast valve is a special and key device of passive reactors such as AP1000, CAP1400 and the like, belongs to a nuclear first-level pressure-bearing component, and has extremely important safety and reliability requirements. The shearing cover is a key component of the work of the explosion valve, the sealing performance of the explosion valve when the explosion valve is closed is guaranteed by means of the closed shearing cover, leakage is guaranteed not to occur, smooth cutting of the shearing cover is guaranteed in an accident phase, opening of a valve is guaranteed, and accidents are prevented from further expanding towards the outside of a nuclear island. In addition, the design specification of the bar material for the cutting cover of the explosion valve is very large, the minimum section diameter is phi 315mm, and the maximum section diameter can reach phi 660mm, so that the manufacturing difficulty is further increased.
The shear cap material was a round bar made of ASME SB-166UNS N06690 alloy, the composition requirements of which are shown in Table 1.
TABLE 1 chemical composition requirements (in weight%) of ASME SB-166UNS N06690 alloy bars
| Element(s) | C | Ni | Cr | Fe | Si | Mn | Cu | S |
| Content (wt.) | ≤0.05 | ≥58.0 | 27.0–31.0 | 7.0–11.0 | ≤0.5 | ≤0.5 | ≤0.5 | ≤0.015 |
However, the technical requirements of the nickel-based alloy bar for the cutting cover of the explosion valve are more strict than those of the ASME SB-166UNS N06690 alloy, not only are the technical indexes such as high-temperature mechanical property at 350 ℃ and intergranular corrosion increased, but also the mechanical properties have upper and lower limits on tensile strength, elongation and yield strength indexes, the more severe is that the product of the tensile strength and the elongation (product of strength and elongation) also has upper and lower limits, the strain rate during tensile test is single-value limited, and the technical requirements are shown in Table 2, for example. As far as the prior art and products are concerned: firstly, the room-temperature tensile elongation is 50-62%, and exceeds the specified upper limit of the table 2, and accordingly the value of the product of strength and elongation Rm multiplied by A does not meet the requirement; secondly, the tensile property at the high temperature of 350 ℃, particularly the yield strength is lower than the standard value; thirdly, the corrosion resistance does not meet the requirement, and the intergranular corrosion rate exceeds 20 mg/square decimeter for a day; fourthly, the specification of the existing forged bar is small, the specification of the conventional ASME SB-166UNS N06690 forged bar product is phi 80 mm-phi 200mm, and the specification requirement of phi 315 mm-phi 660mm cannot be met, and as is well known, the performance can be further reduced after the diameter of the product is enlarged. Therefore, if the cutting cover is smelted according to the composition described in ASME SB-166UNS N06690 and produced according to conventional forging and heat treatment, the design requirements of the cutting cover of the nuclear power explosion valve cannot be met at all. The method is realized by the design of alloy components, an improved forging forming method and an optimized heat treatment process.
TABLE 2 comparison of the main performance indexes of Ni-based alloy for nuclear power equipment and ASME SB-166UNS N06690 alloy bar
Through document inquiry and patent retrieval:
the patent CN201310714808.1 large-size GH690 nickel-based alloy bar billet fine-grain forging method discloses a GH690 alloy bar forging method, the components of the GH690 alloy bar are smelted according to standard components, the specification (cross section) of the bar is small, the forging method is complex, and related contents do not cover the invention.
The patent CN 200810235501.2A Ni-base alloy of steam generator for nuclear power discloses an improved UNSN06600 alloy, the product is a cold-drawn bar or wire, the specification is small, and the components, the manufacturing method and the product specification are not covered by the alloy of the invention.
The patent CN201310472590.3 preparation method of nickel-based alloy for nuclear power station equipment parts discloses a plate-shaped forging with large width-thickness ratio, which is manufactured by adopting a forging production method, and the components, the application, the performance and the product shape do not cover the content of the patent, so that the invention is not in conflict with the invention.
The patent CN201410809408.3 electroslag remelting method for large-size, ultra-pure and high-performance nickel-based alloy 690 discloses a method for producing large-size electroslag remelting ingots by adopting small-size electrodes.
The production method of the nickel-based alloy large-section bar for the shearing cover of the blast valve of the nuclear power key equipment is strictly kept secret by foreign enterprises, and relevant reports and related patent literature documents and introductions are not made.
Through comprehensive comparative analysis, the disclosed information does not cover the present disclosure.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a novel nickel-based alloy with good strong plasticity matching, which is particularly suitable for manufacturing nickel-based alloy bars with ultra-large sections for the shearing cover of the nuclear power station blasting valve.
The invention is realized by the following technical scheme:
a nickel-based alloy for nuclear power key equipment comprises the following elements in percentage by weight:
c: 0.015-0.040%, Cr: 28.0-31.0%, Fe: 7.0-11.0%, W: 0.01-0.15%, V: 0.01-0.15%, and the balance being Ni and unavoidable impurities, wherein the content of Ni is not less than 58%, the content of the unavoidable impurities comprises Mn, Si, P, S, Mo, Nb, Al, Ti, Co, N, Cu and B, and the content of Mn, Si, P, S, Mo, Nb, Al, Ti, Co, N, Cu and B is not more than 0.5%, 0.015%, 0.010%, 0.10%, 0.50%, 0.05%, 0.20% and 0.005%, respectively.
The reason for selecting the chemical composition range of the steel of the present invention is as follows:
carbon (C): too high a carbon content reduces the corrosion properties of the alloy, in particular increases the stress corrosion cracking tendency, while too low a carbon content reduces the mechanical properties, since the deformation of the large-section bars is relatively small, the C content is controlled to 0.015 to 0.040%, preferably 0.018 to 0.030%.
Nickel (Ni): austenitizing forms basic elements, which have good stability in oxidizing and reducing media, have good effects of improving the sensitivity of uniform corrosion and stress corrosion cracking resistance, are also beneficial to improving the plasticity of the material so as to facilitate cold and hot processing, can improve the welding performance of the material, and are generally matched with the contents of Cr and carbon to achieve good effects of resisting intercrystalline corrosion, pitting corrosion and stress corrosion at the same time, but the increase of the content of Ni can obviously improve the cost of the alloy.
Chromium (Cr): cr not only endows the alloy with high-temperature oxidation resistance, but also improves the corrosion resistance of the alloy in high-temperature sulfur-containing gas, is the most important element for stabilizing the surface of the alloy, forms an oxidation-resistant and corrosion-resistant protective layer on the surface of a base material, can prevent the oxidation and hot corrosion of the material, and is generally considered to enable the alloy to have high corrosion resistance by controlling the Cr to be about 30 percent.
Iron (Fe): fe is added mainly for cost control, especially in the production using iron molds and some scrap inevitably contains iron elements. But the Fe element cannot be used in a large amount, otherwise, the corrosion resistance of the alloy is reduced. The invention controls the Fe content to be 8.5-11.0%.
Silicon (Si) and manganese (Mn): the two elements have certain deoxidation effect in the steelmaking process, have certain solid solution strengthening effect, can improve high-temperature mechanical property, and can coordinate the strong plasticity of the alloy by controlling Si and Mn at higher levels under the condition of meeting the technical requirements. Taken together, these two elements are preferably controlled at Si: 0.2-0.4%, Mn: 0.2 to 0.5 percent.
Phosphorus (P) and sulfur (S): s, P is a harmful element of the alloy of the invention, too high content will deteriorate the hot workability of the alloy and easily cause micro segregation, the lower content is better, but the low P raw material cost is high, and P will have a certain regulating effect on the elongation of the alloy, and the alloy manufacturing cost is comprehensively considered, and the P: less than or equal to 0.015, S: in the range of ≦ 0.010, preferably, P: 0.006-0.012%.
Aluminum (Al) and titanium (Ti): AL and Ti have a strengthening effect on the alloy, but too high a content affects hot workability and weldability, and is controlled to be AL: less than or equal to 0.5, S: is less than or equal to 0.5.
Cobalt (Co) and boron (B): co and B are elements which are limited to be added in nuclear power, and the content of the Co and B is required to be controlled to be lower.
Nitrogen (N): n can improve the strength of the material, is easy to form brittle inclusion with elements such as Al, Ti and the like, and is preferably controlled to be 0.005-0.04% in consideration of the comprehensive performance of the toughness of the alloy.
Molybdenum (Mo) and tungsten (W): the trace amount of Mo and W can improve the high-temperature strength of the alloy and can reduce the hot brittleness of the alloy. The reason is that the large atom radius of Mo and W can increase the lattice distortion and lattice atom bond attraction of the solid solution, so that the matrix is strengthened, and the composite addition effect of W and Mo is more obvious.
Vanadium (V) and niobium (Nb): the two elements of V and Nb are easy to form carbide, and a proper amount of V and Nb not only can form fine strengthening phases to improve the strength of the alloy, but also can improve the strengthening effect of Mo and W, and particularly the effect of the composite addition of V and Nb is more obvious.
However, the content of the four elements of Mo, W, V and Nb is too high to form coarse carbides, which are not beneficial to improving the comprehensive properties such as toughness and matching, so that the four trace elements are controlled in the following formula: less than or equal to 0.10%, W: 0.01-0.15%, V: 0.01 to 0.15%, Nb: less than or equal to 0.10 percent; optimized, Mo: 0.01-0.10%; w: 0.02-0.15%; v: 0.02-0.15%; nb: 0.01-0.10%; and Mo + W + V + Nb is less than or equal to 0.4 percent.
The manufacturing method of the nickel-based alloy large-section bar for the nuclear power key equipment comprises the following steps:
preparing nickel-based alloy, hot rolling and forming a bar and carrying out heat treatment on the bar;
the manufacturing method of the nickel-based alloy comprises the following steps: vacuum induction smelting and argon protection electroslag remelting;
the bar forming method comprises multidirectional free forging cogging and large reduction forming;
the heat treatment method is solution heat treatment and supplementary heat treatment.
The vacuum induction smelting can effectively reduce the gas content in the raw materials and obtain the remelting electrode with uniform components. By atmosphere protection electroslag remelting, the solidification structure can be improved, as-cast crystal grains can be refined, the hot working plasticity of an alloy ingot can be improved, the defects of shrinkage cavities, shrinkage porosity and the like in the ingot can be reduced, and the content of non-metal impurities and other impurities in the alloy can be reduced. The manufactured steel ingot is a nickel-based alloy ingot with the phi of 650 and 1000 mm.
The alloy hot working adopts multidirectional free forging, deformation temperature control and high reduction forming technology. The compressive stress in different directions in the multidirectional free forging process can eliminate the microscopic defect of an alloy solidification structure, avoid the generation of deformation dead zones, improve the compactness of the alloy, improve the microscopic segregation of a large high-alloy electroslag ingot and improve the overall uniformity of the structure and the performance. The forging penetration of the large steel ingot can be ensured by controlling the deformation temperature and the large reduction, a fine and uniform dynamic recrystallization structure is formed, and a foundation is laid for the control of the subsequent heat treatment performance.
As a preferred scheme, in the multidirectional free forging cogging, the heating temperature of the alloy steel ingot is 120-200 ℃ below the initial melting point temperature of the alloy, and the heat preservation time is calculated according to the diameter of the steel ingot and specifically comprises the following steps: the heat preservation time is less than or equal to 1min/mm and less than or equal to 0.4 min/mm.
Preferably, in the multidirectional free forging cogging, the forging deformation is square or octagonal, and multidirectional free forging upsetting-drawing-out is performed for 1-3 times. The forging ratio of the alloy can be obviously increased, and the as-cast structure of the steel ingot is fully crushed, so that the large-section bar with good uniformity is obtained.
Preferably, during upsetting, upsetting is carried out for at least 1 time along the three axial directions of the billet, and the upsetting amount is not less than one third of the original axial height of the billet; during drawing, the deformation amount of each fire is 25-65%, the furnace is returned when the temperature is lower than 900 ℃, and the heat preservation temperature of the furnace returned in the last fire is according to the recrystallization temperature t of the alloyRecrystallizationDetermining, specifically: (t)RecrystallizationThe temperature of the last fire return to the furnace is less than or equal to 1 (t) at the temperature of more than or equal to 80 DEG CRecrystallization+150) deg.c and the last deformation of the steel sheet is not lower than 35%. By controlling the large reduction and the low final heat forging temperature, not only needs to prevent the crystal grains from being too large, but also can ensure that the recrystallization can be basically completed in the forging process and the cooling process after forging, and then uniform and fine forging structures can be obtained.
The solution treatment is to fully recrystallize an alloy structure to obtain equiaxed austenite grains with a certain size so as to meet the requirement on mechanical property; furthermore, in order to obtain a single-phase austenite structure, carbides precipitated in the previous process are dissolved into the matrix as much as possible. The solubility of carbide in the matrix is increased along with the increase of the temperature, so that the higher the carbon content is, the higher the solid solution temperature is needed, but the too high solid solution temperature can coarsen crystal grains and reduce the mechanical property, so that the solid solution temperature needs to be determined in a reasonable range according to theoretical calculation and experimental research. The heat preservation time needs to ensure that the temperature of the plate is uniform to ensure that the carbide is fully dissolved in the solution, and the thicker the plate is, the longer the time is needed to ensure that the temperature of the plate is uniform, but alloy crystal grains are coarsened along with the increase of the heat preservation time, so the heat preservation time also needs to be determined in a reasonable range.
The supplementary heat treatment is that after the solution treatment, the carbide is finely and uniformly precipitated after heat preservation for a certain time at a certain temperature, and the corrosion resistance of the alloy can be obviously improved. However, because the carbides are mainly rich in chromium, and the diffusion speed of chromium in the matrix is low, the precipitation of the chromium causes the appearance of a structure chromium-poor area, so that the corrosion resistance of the alloy is obviously reduced, therefore, longer heat preservation time is needed to ensure that the chromium is fully diffused, the grade boundary chromium-poor degree caused by the formation of grain boundary carbides is improved, the balance is basically achieved after the time reaches a certain length, the prolonging effect is not obvious, and the time is not longer to reduce the production cost. The carbide precipitation can only occur at a certain temperature, the precipitation cannot be performed due to low precipitation power when the temperature is too high, the precipitation is slow when the temperature is too low, and the optimal precipitation temperature and the sufficient precipitation time can be determined through experimental research.
Preferably, the temperature of the solution heat treatment is set according to the carbon element content in the nickel-based alloy, and specifically comprises the following steps:
when the content of the carbon element is lower than 0.020%, the solution heat treatment temperature is 1030-1050 ℃;
when the content of the carbon element is not less than 0.020% and less than 0.025%, the solution heat treatment temperature is 1050-1070 ℃;
when the content of the carbon element is not less than 0.025 percent and less than 0.030 percent, the solution heat treatment temperature is 1070 to 1090 ℃;
when the content of the carbon element is not less than 0.030 percent, the solution heat treatment temperature is 1090-1110 ℃.
Preferably, the holding time of the solution heat treatment is set according to the diameter D of the bar, and specifically comprises the following steps:
when the diameter D of the bar is less than 450mm, the heat preservation time of the solution heat treatment is T ═ 0.5 +/-0.2D, min;
when the diameter D of the bar is more than or equal to 450mm, the heat preservation time of the solution heat treatment is (0.45 +/-0.2) D, min.
Preferably, the heat preservation temperature of the supplementary heat treatment is 705-745 ℃, and the heat preservation time is 8-13 h.
Preferably, the heat preservation temperature of the supplementary heat treatment is 710-735 ℃, and the heat preservation time is 10-12 h.
The novel nickel-based alloy large-section bar with fine and uniform structure, good corrosion resistance, and good strength and plasticity can be obtained by the process control, and the special application technical requirements of the cutting cover of the explosion valve are completely met.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the existing ASME SB-166 UNSN06690 alloy bar, the novel nickel-based alloy bar for nuclear power key equipment provided by the invention has the following advantages: elements such as Mo, W, V, Nb and the like which influence the room temperature and high temperature performance of the alloy are added in a controlled manner, elements such as C, P, N, Si, Mn and the like which influence the plasticity of the alloy are strictly controlled, and the strength and the plasticity of the alloy are adjusted through a microalloying strengthening and toughening mechanism on the premise of ensuring excellent corrosion resistance, so that the best combination of strong plasticity and the like which is suitable for the use requirement of nuclear power equipment can be achieved.
2. The invention adopts a large nickel-based alloy electroslag ingot with the diameter of 650 plus 1000mm, can ensure that the large-section bar has sufficient forging ratio, and is the basic guarantee of the mechanical property.
3. The manufacturing process changes the traditional production mode of repeated upsetting-stretching for multiple times, introduces the free forging technology of multi-axial upsetting-stretching, adopts the technology of controlling the deformation temperature and the large reduction, can avoid the deformation dead zone, and improves the deformation uniformity and the forging permeability, thereby obtaining the large-section bar with good integral uniformity and fine and uniform tissue.
4. The bar manufactured by the alloy and the manufacturing method thereof is far higher than the performance requirement of an ASME SB-166 UNSN06690 alloy bar, the defect that the high plasticity index exceeds the standard requirement is overcome, the novel nickel-based alloy has excellent high plasticity matching and corrosion resistance through component design and processing process optimization, can be used under the working condition of 350 ℃ for a long time, meets the design life requirement of nuclear power equipment for 60 years, is more suitable for nuclear power key equipment, and has wide and urgent application prospect in the fields of nuclear power and the like.
5. The manufacturing process is particularly suitable for manufacturing the nickel-based alloy bar with the large cross section of phi 300 mm-phi 660mm, is completely suitable for key parts of nuclear island equipment of a nuclear power station, and has important significance for effectively promoting the autonomous construction of large nuclear power stations in China.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
According to the components of the invention, an alloy electrode bar is smelted and cast by vacuum induction, and is remelted into an electroslag remelting steel ingot with the diameter of 650mm by adopting an argon protection electroslag remelting furnace, and the obtained alloy components are shown in Table 3.
Heating and preserving heat of a large electroslag remelting steel ingot at 1150 ℃ for 5 hours, then discharging and forging, upsetting for 1 time in three axial directions respectively, and ensuring the deformation (30 +/-5)% of each firing time of drawing; and finally, heating the steel bar for the last fire time at 1050 ℃, and finally forging the steel bar into a bar with the diameter of 330mm, wherein the deformation is 40%. Keeping the solution heat treatment temperature at 1035 ℃ for 150 min; and performing supplementary heat treatment at 730 ℃ and keeping the temperature for 10 hours. The properties of the bars are shown in table 4.
Example 2
According to the components of the invention, an alloy electrode bar is smelted and cast by vacuum induction, and is remelted into an electroslag remelting steel ingot with the diameter of 900mm by adopting an argon protection electroslag remelting furnace, and the obtained alloy components are shown in Table 3.
Heating and preserving heat of a large electroslag remelting steel ingot at 1200 ℃ for 8 hours, then discharging and forging, upsetting for 2 times in the three axial directions respectively, and ensuring the deformation (40 +/-5)% of each firing time of drawing; and finally, heating the steel bar by the last fire at the temperature of 1080 ℃ and the deformation of the steel bar is 50 percent, and finally forging the steel bar into a bar with the diameter of 450 mm. The temperature of the solution heat treatment is 1060 ℃, and the temperature is kept for 240 min; and performing supplementary heat treatment at 720 ℃, and keeping the temperature for 10 hours. The properties of the bars are shown in table 4.
Example 3
According to the components of the invention, an alloy electrode bar is smelted and cast by vacuum induction, and is remelted into an electroslag remelting steel ingot with the diameter of 900mm by adopting an argon protection electroslag remelting furnace, and the obtained alloy components are shown in Table 3.
Heating and preserving heat of a large electroslag remelting steel ingot at 1150 ℃ for 8 hours, then discharging and forging, upsetting 2 times in the three axial directions respectively, and ensuring the deformation (50 +/-5)% of each firing time of drawing; the last heating time is 1040 ℃, the deformation amount is 45 percent, and the bar with the diameter of 530mm is finally forged. The temperature of the solution heat treatment is 1080 ℃, and the temperature is kept for 260 min; and performing supplementary heat treatment at 725 ℃, and keeping the temperature for 11 h. The properties of the bars are shown in table 4.
Example 4
According to the components of the invention, an alloy electrode bar is smelted and cast by vacuum induction, and is remelted into an electroslag remelting steel ingot with the diameter of 1000mm by adopting an argon protection electroslag remelting furnace, and the obtained alloy components are shown in Table 3.
Heating and preserving heat of a large electroslag remelting steel ingot at 1220 ℃ for 12 hours, then discharging and forging, carrying out co-upsetting 3 times along the height of the steel ingot in the axial direction, respectively upsetting 2 times along the other two axial directions, and ensuring the deformation (50 +/-10)% of each heating time of drawing; the last heating time is 1040 ℃, the deformation amount is 50 percent, and the bar with the diameter of 650mm is finally forged. The solution heat treatment temperature is 1060 ℃, and the temperature is kept for 310 min; and performing supplementary heat treatment at 720 ℃, and keeping the temperature for 11.5 h. The properties of the bars are shown in table 4.
According to 4 embodiments produced by the chemical components and the production method designed by the invention, the size, appearance, chemical components, mechanical properties, product of strength and elongation and corrosion resistance of the produced large-section nickel-based alloy bar all meet the technical requirements of the nickel-based alloy for nuclear power equipment. Further, as can be seen from the comparison between tables 3 and 4, the novel nickel-based alloy disclosed by the invention has better comprehensive performance, all technical indexes can simultaneously meet the requirements of nuclear power equipment, the phenomenon of 'considering each other' can not occur, and the alloy bar, no matter the components or the performance, better meets the technical requirements of the nuclear power equipment than the UNS N06690 alloy bar produced according to ASME SB-166.
TABLE 3 chemical composition (in weight percent) of nickel-base alloy bars
Note: in the table, "- -" is not required.
TABLE 4 Properties of Nickel-base alloy bars
In summary, the present invention is only a preferred embodiment, and not intended to limit the scope of the invention, and all equivalent changes and modifications in the shape, structure, characteristics and spirit of the present invention described in the claims should be included in the scope of the present invention.
Claims (6)
1. A manufacturing method of a nickel-based alloy large-section bar for nuclear power key equipment is characterized by comprising the following steps:
preparing nickel-based alloy, hot-forming a bar and carrying out heat treatment on the bar;
the manufacturing method of the nickel-based alloy comprises the following steps: vacuum induction smelting and argon protection electroslag remelting;
the bar forming method comprises multidirectional free forging cogging and large reduction forming;
the heat treatment method of the bar comprises solution heat treatment and supplementary heat treatment,
in the multidirectional free forging cogging, the heating temperature of the alloy steel ingot is 120-200 ℃ below the initial melting point temperature of the alloy, and the heat preservation time is calculated according to the diameter of the steel ingot and specifically comprises the following steps: the heat preservation time is less than or equal to 1min/mm and is less than or equal to 0.4 min/mm;
in the multidirectional free forging cogging, forging deformation adopts a square or octagonal shape, and multidirectional free forging upsetting-drawing-out is carried out for 1-3 times;
during said upsetting, the blank is flangedUpsetting the billet in three axial directions for at least 1 time, wherein the upsetting amount is not less than one third of the original axial height of the billet; during drawing, the deformation amount of each fire is 25-65%, the furnace is returned when the temperature is lower than 900 ℃, and the heat preservation temperature of the furnace returned in the last fire is according to the recrystallization temperature t of the alloyRecrystallizationDetermining, specifically: (t)RecrystallizationThe temperature of the last fire returning to the furnace is less than or equal to (t) 80 DEG CRecrystallization+150) DEG C, the last heat deformation is not less than 35%,
the nickel-based alloy large-section bar comprises the following elements in percentage by weight: c: 0.015-0.040%, Cr: 28.0-31.0%, Fe: 7.0-11.0%, W: 0.01-0.15%, V: 0.01-0.15%, and the balance being Ni and unavoidable impurities, wherein the content of Ni is not less than 58%, the content of the unavoidable impurities comprises Mn, Si, P, S, Mo, Nb, Al, Ti, Co, N, Cu and B, and the content of Mn, Si, P, S, Mo, Nb, Al, Ti, Co, N, Cu and B is not more than 0.5%, 0.015%, 0.010%, 0.10%, 0.50%, 0.05%, 0.20% and 0.005%, respectively.
2. The method for manufacturing the nickel-based alloy large-section bar according to claim 1, wherein the weight percentages of the elements are respectively as follows:
c: 0.018-0.030%, Cr: 28.5-30.5%, Fe: 8.5-11.0%, Ni: 58.0-63.0%, W: 0.02-0.15%, V: 0.02 to 0.15%, Mn: 0.1 to 0.5%, Si: 0.1-0.4%, P: 0.003-0.012%, S: less than or equal to 0.005%, Mo: 0.01 to 0.10%, Nb: 0.01-0.10%, Al: less than or equal to 0.40 percent, Ti: less than or equal to 0.40%, Co: less than or equal to 0.03%, N: 0.005-0.04%, wherein the sum of the contents of Mo, W, V and Nb is not more than 0.4%.
3. The method for manufacturing the nickel-based alloy large-section bar according to claim 1, wherein the holding temperature of the solution heat treatment is set according to the carbon element content in the nickel-based alloy, and specifically comprises the following steps:
when the content of the carbon element is lower than 0.020%, the solution heat treatment temperature is 1030-1050 ℃;
when the content of the carbon element is not less than 0.020% and less than 0.025%, the solution heat treatment temperature is 1050-1070 ℃;
when the content of the carbon element is not less than 0.025 percent and less than 0.030 percent, the solution heat treatment temperature is 1070 to 1090 ℃;
when the content of the carbon element is not less than 0.030 percent, the solution heat treatment temperature is 1090-1110 ℃.
4. The method for manufacturing a large-section bar of nickel-base alloy according to claim 1, characterized in that the holding time of the solution heat treatment is set according to the diameter D of the bar, and specifically:
when the diameter D of the bar is less than 450mm, the solution heat treatment heat preservation time is T = (0.5 +/-0.2) D, min;
when the diameter D of the bar is more than or equal to 450mm, the solution heat treatment heat preservation time is T = (0.45 +/-0.2) D, min.
5. The method for manufacturing the nickel-based alloy large-section bar according to claim 1, wherein the heat preservation temperature of the supplementary heat treatment is 705-745 ℃, and the heat preservation time is 8-13 hours.
6. The method for manufacturing the nickel-based alloy large-section bar according to claim 5, wherein the heat preservation temperature of the supplementary heat treatment is 710-735 ℃, and the heat preservation time is 10-12 hours.
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| CN110273085B (en) * | 2019-04-15 | 2022-01-07 | 上海大学 | Gadolinium-rich nickel-based alloy material for reactor spent fuel storage and preparation method thereof |
| CN110373573B (en) * | 2019-08-13 | 2021-06-04 | 上海大学 | Gadolinium-rich nickel-tungsten-based alloy material for nuclear shielding and preparation method thereof |
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| CN110760718B (en) * | 2019-11-25 | 2021-01-15 | 北京科技大学 | Preparation method of high-tungsten high-cobalt nickel alloy high-purity fine-grain bar |
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