CN117210771B - Thick high-performance nitrogen-containing austenitic stainless steel for nuclear power and manufacturing method thereof - Google Patents
Thick high-performance nitrogen-containing austenitic stainless steel for nuclear power and manufacturing method thereof Download PDFInfo
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- 239000010959 steel Substances 0.000 claims abstract description 79
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Abstract
The invention provides a thick high-performance nitrogen-containing austenitic stainless steel for nuclear power and a manufacturing method thereof, wherein the steel plate comprises the following ：C：0.01％～0.03％;Si：0.50％～0.70％;Mn：4.00％～5.00％;P≤0.030％;S≤0.015％;Ni：9.10％～9.90％;Cr：18.00％～20.00％;Mo：3.50％～4.50％;Al：≤0.010％;Nb：0.26％～0.35％;Ti：0.15％～0.20％,N：0.12％～0.16％; parts by weight of Fe and unavoidable impurities; the manufacturing method comprises smelting, continuous casting, rolling and solution treatment; after the steel grade is subjected to solution treatment, the elongation percentage A 50 after the steel plate is broken at the normal temperature and the high temperature of 350 ℃ is more than or equal to 39.5 percent. The reduction of area is more than or equal to 59.5 percent, completely meets the index requirement, and has larger allowance.
Description
Technical Field
The invention belongs to the field of metal materials, and particularly relates to thick-specification high-performance nitrogen-containing austenitic stainless steel for nuclear power and a manufacturing method thereof.
Background
Nuclear energy is an important energy source used by countries in the world due to various advantages such as cleanliness, economy and the like, and is an important component part of a primary energy consumption structure in developed countries in the world. Since the nuclear power station consumes little nuclear fuel during operation, a large amount of electric energy can be generated, which is far higher in power generation efficiency than thermal power generation. Therefore, the development of nuclear power is a necessary choice for optimizing the electric power industry structure, realizing the energy source guarantee diversification and improving the comprehensive economical strength, the industrial technical level and the international status of China.
In key parts of a nuclear power station, under the extreme service conditions of neutron irradiation, cooling medium corrosion and the like, the austenitic stainless steel has good mechanical property, corrosion resistance, tissue stability and irradiation resistance, is used as steel grade meeting the above conditions, and is widely applied to large-scale pressure vessels such as nuclear reactor pressure vessels, steam generators, voltage regulators and the like in the nuclear power station.
Related patents for nitrogen-containing austenitic stainless steel currently produced are as follows:
Patent application number 201310234968.6 of Zhejiang Daron alloy steel limited company, namely 'production method of austenitic stainless steel for nuclear power of 316 LN', publication number CN 103320718 B,C≤0.020％、Mn≤2.00％、Si≤0.75％、P≤0.025％、S≤0.005％、Cr：16.00～18.00％、Ni：11.00～14.00％、Mo：2.00～3.00％、Cu≤0.10％、Co≤0.050％、N：0.10～0.16％, and the balance of Fe. The manufacturing method adopts electric furnace, vacuum refining, forging, annealing, quenching and tempering heat treatment. The steel plate produced by the method has good room temperature mechanical property, the yield strength Rp0.2 reaches 233Mpa, and the tensile strength Rm reaches 558Mpa. However, in the claims of the comparison document, the 316LN steel is produced by adopting a forging method, and the two aspects of material uniformity and manufacturing cost are different from the rolled steel plate to a certain extent, and the yield strength is 233MPa, the tensile strength is only 558MPa and the comprehensive performance is poor.
Patent application number 202110363149.6 of Shanxi Tai steel stainless steel, the rest of publication number CN 113088822A,C≤0.03％,Si≤1.00％,Mn：3.00～6.00％,P≤0.030％,S≤0.015％,Cr：18.00～23.00％,Ni：12.00～18.00％,Mo：2.00～4.00％,N：0.20～0.30％,Nb：0.15～0.25％, is Fe and unavoidable impurities, and the name of the patent application is 'high nitrogen, high strength and low magnetic austenitic stainless steel middle plate and manufacturing method thereof'. The yield strength of the steel plate with the thickness of 8mm is more than or equal to 480MPa, the tensile strength is more than or equal to 790MPa, and the impact at minus 40 ℃ is more than or equal to 119J, but the chemical components of the steel plate are different from those of the steel plate, and the steel plate adopts a high-nitrogen design, so that the smelting control difficulty and the smelting control cost are increased. The invention only provides the mechanical property of the steel plate with the thickness of 8mm, and meanwhile, the invention does not consider the high-temperature mechanical property and can not meet the requirements of the steel for the reactor nuclear station.
Patent application number 202111210754.6, publication number CN 113943903 A,C≤0.02％、Si≤1.00％、Mn≤1.00％、P≤0.03％、S≤0.005％、Cr：19.0～24.0％、Ni：17.0～25.0％、Mo：5.5～6.5％、Cu：0.5～1.5％、N：0.15～0.30％、B：0.003～0.005％、Ce：0.003～0.007％, and the balance of Fe and other unavoidable impurity elements of "low precipitation phase precipitation super austenitic stainless steel and preparation and heat treatment method thereof" applied by Tai principle university. Can obviously inhibit precipitation of Cr-rich and Mo-rich hard brittle sigma phases, and obtain the austenitic stainless steel with better corrosion resistance and better thermoplasticity. However, the invention has higher Cr, ni and other alloy components, higher production and manufacturing cost due to the addition of rare earth elements, and does not provide mechanical property and corrosion resistance parameters.
Disclosure of Invention
The invention aims to overcome the problems and the shortcomings and provide thick-specification high-performance nitrogen-containing austenitic stainless steel for nuclear power with good comprehensive mechanical properties and internal quality and a manufacturing method thereof.
The invention aims at realizing the following steps:
a thick high-performance nitrogen-containing austenitic stainless steel for nuclear power comprises the following ：C：0.01％～0.03％;Si：0.50％～0.70％;Mn：4.00％～5.00％;P≤0.030％;S≤0.015％;Ni：9.10％～9.90％;Cr：18.00％～20.00％;Mo：3.50％～4.50％;Al：≤0.010％;Nb：0.26％～0.35％;Ti：0.15％～0.20％,N：0.12％～0.16％; parts by weight of Fe and unavoidable impurities.
Further; cr in the stainless steel: si=28.0 to 37.0.
Further; ti in the stainless steel: n=1.10 to 1.50.
Further; the microstructure of the steel plate is fine austenite, and the grain size is 7-9 grades; the steel plate also comprises TiN second phase particles with the size of 5-20 nm.
Further; the thickness of the stainless steel plate is 20-60mm.
Further; the thickness of the stainless steel plate is 20-60 mm; the yield strength Rp 0.2 is more than or equal to 302MPa, and the tensile strength R m is more than or equal to 576MPa; the tensile yield strength Rp 0.2 is more than or equal to 176MPa, and the tensile strength R m is more than or equal to 469MPa at the high temperature of 350 ℃; low-temperature impact KV 8 at minus 196 ℃ is more than or equal to 278J.
The reason for designing the components of the invention is as follows:
(1) C: the content of carbon in the stainless steel and the distribution form thereof are largely related to the performance and structure of the stainless steel: carbon can stabilize austenite elements, has a great degree of action, is about 30 times of nickel, and can remarkably improve the mechanical properties of steel. However, as the carbon content in the steel increases, the more chromium forms carbides with the carbon, which reduces the corrosion resistance of the steel. The carbon content in the steel is not too high, so the content of C in the invention is controlled to be in the range of 0.01-0.03%.
(2) Si: the Si atoms can form solid solution in an austenite lattice in a substitution form, so that lattice distortion is generated, the solid solution strengthening effect is achieved, the strength of the steel is improved, and the Si can improve the oxidation resistance of the steel. Meanwhile, si element has the function of stabilizing irradiation defects, and is beneficial to prolonging the service life of nuclear power equipment. However, when the Si addition amount exceeds 3%, the plasticity and toughness of the steel are remarkably reduced, so that the Si content in the steel is required to be controlled to 0.50 to 0.70%, while Cr: the ratio of the content of the alloy elements of Si is controlled between 28.0 and 37.0 so as to ensure that the steel plate has good toughness and excellent corrosion resistance.
(3) Mn: in stainless steel, manganese remains in the steel as a deoxidizing element, and an important role of manganese is to be integrated into nickel-saving stainless steel and high-nitrogen stainless steel, wherein manganese replaces nickel to save nickel resources, and simultaneously to increase the solubility of nitrogen and improve the solubility of nitrogen. Another important role of manganese is to form MnS, inhibit the deleterious effects of sulfur, and improve the high temperature hot plasticity of high chromium nickel austenitic stainless steel. However, the increase of Mn content reduces the corrosion resistance and the toughness of stainless steel, and the Mn content in the steel is required to be controlled within a proper range, namely, controlled to be 4.00-5.00%.
(4) Ni: in the nickel content range where martensitic transformation is possible, as the nickel content increases, the strength of the steel decreases and the plasticity increases. When the austenitic stainless steel has stable austenitic structure, the addition of nickel can further improve the plasticity and toughness of the austenitic stainless steel, and the austenitic stainless steel has better stainless property and corrosion resistance; however, an increase in nickel content results in an increase in the intergranular corrosion susceptibility of austenitic stainless steel. Therefore, the present invention requires that Ni content in steel is controlled to 9.10-9.90%.
(5) Cr: in austenitic stainless steels, the interaction of chromium and nickel forms a stable austenitic structure, and in single austenitic stainless steels the chromium content does not have a significant effect on the mechanical properties. The Cr element causes the electrode potential of the steel to suddenly change from a negative potential to a positive electrode potential. Thus the corrosion resistance of the steel can be significantly improved. Therefore, the present invention requires that the Cr content in the steel be controlled to 18.00-20.00%.
(6) Mo: mo is an important alloying element widely used in stainless steel. In austenitic stainless steel, mo has a remarkable solid solution strengthening effect. And the interaction of Mo and Cr element can obviously improve the corrosion resistance of stainless steel, so the invention requires that the Mo content in the steel is controlled to be 3.50-4.50%.
(7) Al: al can obviously improve the oxidation resistance of steel and reduce smelting cost. Researches show that the mechanical properties of the steel can be improved by adding a proper amount of Al into the austenitic steel. However, since an increase in Al content lowers the toughness of the steel, the present invention requires that the Al content in the steel be controlled to 0.010% or less.
(8) Nb: nb can improve the yield strength of steel, reduce the brittle transition temperature, is beneficial to the welding performance of steel, and has poor sensitivity to irradiation, so the Nb content of the steel is required to be controlled to be 0.26-0.35%.
(9) Ti: ti can form carbide and nitride, and can reduce precipitation of Cr 23 C6 in steel. The TiC and TiN are finely dispersed and distributed to serve as cores for austenite nucleation and growth, so that the effect of grain refinement is achieved, meanwhile, the TiC and the TiN block dislocation movement, and the strength of austenite can be remarkably improved. Therefore, the invention requires that the content of N element in steel is controlled between 0.12 and 0.16 percent, ti: the ratio of the content of the alloy elements of N is controlled to be 1.10-1.50, and Ti and N elements are added according to the proportion, so that the formation of TiN and TiC compounds is facilitated. On the other hand, the porosity is ensured to be at a lower level, and the steel plate is ensured to have good surface quality.
(10) P: p is a harmful element, which causes the brittleness of the steel to be increased, and also causes the yield point and the yield ratio to be significantly improved, and the plasticity and the toughness to be deteriorated, thereby adversely affecting welding. Meanwhile, the irradiation test shows that the P is very sensitive to irradiation embrittlement, so that the lower the P content in the steel is required to be, the better the P content is, and the lower the P content is required to be, the invention is required to be less than 0.030 percent.
(11) S: s forms FeS and MnS sulfides at austenite grain boundaries in steel, which reduce the impact toughness and weldability of steel, and S also tends to accelerate irradiation embrittlement. Therefore, the S content in the steel should be limited to 0.015% or less.
(12) N: n is a solid solution forming element and can act to stabilize austenite, with an ability of about 40 times that of Ni. However, too high N can form defects such as air holes in the smelting process, and the surface quality of the steel plate is affected. Therefore, the invention requires that the content of N element in the steel is controlled between 0.12 and 0.16 percent.
The second technical scheme of the invention is to provide a manufacturing method of thick high-performance nitrogen-containing austenitic stainless steel for nuclear power, smelting, continuous casting, rolling and solution treatment;
(1) Smelting and continuous casting:
To ensure the quality of continuous casting, the casting blank segregation is controlled and loosened. Adopting high-quality waste carbon steel to perform EAF electric furnace smelting, controlling the content of N element by an AOD converter, controlling the tapping temperature by an LF furnace to be 1505-1515 ℃, controlling the superheat degree of a tundish to be 15-25 ℃, controlling the continuous casting drawing speed to be 1.0-1.2 m/min, and controlling the thickness of the section of a casting blank to be 195-210 mm.
(2) Rolling:
The two-stage rolling technology is adopted, the billet heating temperature is 1180-1250 ℃, the heat preservation time is 3-4 min/mm, the billet is uniformly heated, and sufficient hot working temperature is provided for the rolling process. The one-stage rolling temperature is controlled above the recrystallization temperature to break the dendrite of casting blank, reduce segregation and uniform structure, and simultaneously provide recrystallization driving force, so that recrystallized grains in the structure take nano-scale second phase particles such as TiN, tiC and the like as nucleation points, promote the growth of the grains, and achieve the effect of refining the grains. Therefore, the initial rolling temperature of one stage is controlled to 1150-1195 ℃, the final rolling temperature is controlled to 1050-1100 ℃, and the single-pass reduction rate is controlled to 15-22%. The two-stage rolling is controlled at a temperature lower than the recrystallization temperature, so that the steel plate is fully deformed, and a large amount of deformation energy is introduced, thereby facilitating the formation of crystal grains in the subsequent solution treatment process. Therefore, the two-stage rolling temperature is controlled to 970-1000 ℃, the finishing temperature is controlled to 920-960 ℃, and the single-pass reduction rate is controlled to 5-10%; and naturally cooling the steel plate after rolling.
(3) Solution treatment:
The solid solution temperature is 1060+/-10 ℃, the solid solution cleaning and heat preserving time is 1.5-2.0 min/mm, and then the solid solution is rapidly cooled, and the cooling speed is 7-10 ℃/s; the solid solution treatment is adopted, and the higher temperature and the longer temperature are selected for heat preservation, so that elements such as Si, ni and the like are fully dissolved into the Fe matrix, and the supersaturated solid solution is formed to improve the performance of the steel. On the other hand, the heat preservation is carried out at a higher temperature, so that the deformation introduced in the rolling process can interact, the formation and growth of crystal grains are promoted, and uniform and fine austenite crystal grains are obtained. After the solution treatment is completed, the steel plate is rapidly cooled in water at a cooling rate of 7-10 ℃ per second to reduce the formation of precipitated phases.
The invention has the beneficial effects that:
(1) The product produced by the process has excellent strength index through alloying treatment and solution treatment. The yield strength (Rp 0.2) is more than or equal to 302MPa and the tensile strength (R m) is more than or equal to 576MPa after solution treatment; the high-temperature tensile yield strength (Rp 0.2) at 350 ℃ is more than or equal to 176MPa and the tensile strength (R m) is more than or equal to 469MPa. The tensile properties of the steel plates with different thicknesses are far higher than the index requirements, and compared with other steel types, the tensile properties of the steel plates with different thicknesses are greatly improved, so that the mechanical property requirements under different service conditions can be met.
(2) After the steel grade is subjected to solution treatment, the impact absorption power at minus 196 ℃ is more than or equal to 278J, and the steel grade is kept at a higher level. Completely meets the requirements of indexes and has larger allowance.
(3) After the steel grade is subjected to solution treatment, the elongation percentage A 50 after the steel plate is broken at the normal temperature and the high temperature of 350 ℃ is more than or equal to 39.5 percent. The reduction of area is more than or equal to 59.5 percent, completely meets the index requirement, and has larger allowance.
(4) The steel grade of the invention can effectively control the segregation of the internal components of the tissue through reasonable smelting, rolling and heat treatment process control, and simultaneously form tiny dispersed second phase particles. The internal structure with finer austenite grain size and smaller inclusion size can be obtained, and the composite material has excellent comprehensive mechanical properties.
Detailed Description
The invention is further illustrated by the following examples.
According to the component proportion of the technical scheme, smelting, continuous casting, rolling and solution treatment are carried out.
(1) Rolling:
The billet heating temperature is 1180-1250 ℃, and the heat preservation time is 3-4 min/mm; the initial rolling temperature of the first stage is 1150-1195 ℃, the final rolling temperature is 1050-1100 ℃, and the single-pass reduction rate is 15-22%; the two-stage rolling temperature is 970-1000 ℃, the finish rolling temperature is 920-960 ℃, and the single-pass reduction rate is 5-10%; naturally cooling the steel plate after rolling;
(2) Solution treatment:
The solid solution temperature is 1060+/-10 ℃, the solid solution cleaning and heat preserving time is 1.5-2.0 min/mm, and then the cooling is fast, and the cooling speed is 7-10 ℃/s.
Further; in the smelting process, the LF furnace controls the tapping temperature to be 1505-1515 ℃ and the superheat degree of the tundish to be 15-25 ℃;
in the continuous casting process, the continuous casting drawing speed is controlled to be 1.0-1.2 m/min, and the thickness of the section of the casting blank is 195-210 mm.
The composition of the steel of the example of the invention is shown in Table 1. The main technological parameters of the smelting and continuous casting of the steel of the embodiment of the invention are shown in Table 2. The main technological parameters of the rolling of the steel of the embodiment of the invention are shown in Table 3. The room temperature and low temperature mechanical properties of the inventive example steels are shown in Table 4. The high temperature mechanical properties of the steel of the example of the invention at 350 ℃ are shown in Table 5.
TABLE 1 composition (wt%) of the inventive example steel
TABLE 2 main process parameters for smelting and continuous casting of the inventive example steel
| Examples | Thickness of steel plate is mm | Tapping temperature of LF furnace at DEG C | Continuous casting drawing speed m/min | Thickness of continuous casting blank section mm |
| 1 | 20 | 1235 | 1165 | 196 |
| 2 | 30 | 1230 | 1160 | 199 |
| 3 | 40 | 1200 | 1150 | 202 |
| 4 | 50 | 1220 | 1150 | 205 |
| 5 | 60 | 1250 | 1155 | 209 |
| 6 | 20 | 1198 | 1152 | 195 |
| 7 | 30 | 1215 | 1170 | 200 |
| 8 | 40 | 1240 | 1190 | 203 |
| 9 | 50 | 1245 | 1195 | 207 |
| 10 | 60 | 1250 | 1190 | 210 |
TABLE 3 main process parameters for rolling the inventive example steel
TABLE 4 Properties of the inventive example Steel
TABLE 5 high temperature Performance at 350 ℃ of the inventive example Steel
| Examples | Rp0.2,MPa | Rm,MPa | A,％ | Z,％ |
| 1 | 201 | 497 | 42.0 | 65.0 |
| 2 | 194 | 492 | 44.0 | 63.0 |
| 3 | 186 | 479 | 43.0 | 64.0 |
| 4 | 183 | 483 | 50.0 | 70.5 |
| 5 | 176 | 469 | 42.0 | 62.0 |
| 6 | 195 | 492 | 37.0 | 59.5 |
| 7 | 192 | 487 | 36.0 | 58.0 |
| 8 | 190 | 481 | 36.0 | 57.5 |
| 9 | 180 | 475 | 35.0 | 56.5 |
| 10 | 178 | 470 | 35.0 | 55.5 |
The performance indexes of the steel plate produced by the method completely meet the requirements, and meanwhile, the steel plate has good high-temperature performance and good toughness and strength matching, the room-temperature yield strength Rp 0.2 is more than or equal to 302MPa, and the tensile strength R m is more than or equal to 576MPa; the tensile yield strength Rp 0.2 of the steel plate at the high temperature of 350 ℃ is more than or equal to 176MPa, and the tensile strength R m is more than or equal to 469MPa; the low-temperature impact absorption power KV 8 is more than or equal to 278J at the temperature of minus 196 ℃ and completely meets the performance requirements of the nuclear power steel of the reactor.
The present invention has been properly and fully described in the foregoing embodiments by way of example only, and not by way of limitation, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, any modification, equivalent substitution, improvement, etc. should be included in the scope of the invention, and the scope of the invention is defined by the claims.
Claims (7)
1. A thick high-performance nitrogen-containing austenitic stainless steel for nuclear power is characterized in that the stainless steel comprises the following ：C：0.01％～0.03％;Si：0.50％～0.70％;Mn：4.00％～5.00％;P≤0.030％;S≤0.015％;Ni：9.10％～9.90％;Cr：18.00％～20.00％;Mo：3.50％～4.50％;Al：≤0.010％;Nb：0.26％～0.35％;Ti：0.15％～0.20％,N：0.12％～0.16％; parts by weight of Fe and unavoidable impurities; the thickness of the stainless steel plate is 20-60 mm; the yield strength Rp 0.2 is more than or equal to 302MPa, and the tensile strength R m is more than or equal to 576MPa; the tensile yield strength Rp 0.2 is more than or equal to 176MPa, and the tensile strength R m is more than or equal to 469MPa at the high temperature of 350 ℃; low-temperature impact KV 8 at minus 196 ℃ is more than or equal to 278J.
2. The thick gauge high performance nitrogen containing austenitic stainless steel for nuclear power of claim 1, wherein Cr: si=28.0 to 37.0.
3. The thick gauge high performance nitrogen containing austenitic stainless steel for nuclear power of claim 1, wherein Ti: n=1.10 to 1.50.
4. The thick high-performance nitrogen-containing austenitic stainless steel for nuclear power according to claim 1, wherein the microstructure of the stainless steel is fine austenite, and the grain size is 7-9 grades.
5. The thick gauge high performance nitrogen containing austenitic stainless steel for nuclear power of claim 4, further comprising TiN second phase particles ranging from 5 to 20 nm.
6. A method for manufacturing a thick high-performance nitrogen-containing austenitic stainless steel for nuclear power according to any one of claims 1 to 5, comprising smelting, continuous casting, rolling, solution treatment; the method is characterized in that:
(1) Rolling:
The billet heating temperature is 1180-1250 ℃, and the heat preservation time is 3-4 min/mm; adopting two-stage rolling, wherein the initial rolling temperature of one stage is 1150-1195 ℃, the final rolling temperature is 1050-1100 ℃, and the single-pass reduction rate is 15-22%; the two-stage rolling temperature is 970-1000 ℃, the finish rolling temperature is 920-960 ℃, and the single-pass reduction rate is 5-10%; naturally cooling the steel plate after rolling;
(2) Solution treatment:
The solid solution temperature is 1060+/-10 ℃, the solid solution cleaning and heat preserving time is 1.5-2.0 min/mm, and then the cooling is fast, and the cooling speed is 7-10 ℃/s.
7. The method for manufacturing the thick-gauge high-performance nitrogen-containing austenitic stainless steel for nuclear power according to claim 6, wherein the method comprises the following steps:
In the smelting process, the LF furnace controls the tapping temperature to be 1505-1515 ℃ and the superheat degree of the tundish to be 15-25 ℃;
in the continuous casting process, the continuous casting drawing speed is controlled to be 1.0-1.2 m/min, and the thickness of the section of the casting blank is 195-210 mm.
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