CN113061802A - High-strength austenitic aged stainless steel resistant to corrosion of concentrated nitric acid containing oxidative ions and preparation method thereof - Google Patents
High-strength austenitic aged stainless steel resistant to corrosion of concentrated nitric acid containing oxidative ions and preparation method thereof Download PDFInfo
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Abstract
The invention relates to high-strength austenitic aging stainless steel resistant to concentrated nitric acid corrosion of oxidizing ions and a preparation method thereof, belonging to the technical field of materials. The high-strength austenitic aged stainless steel comprises the following chemical components in percentage by weight: 16.0 to 20.0% of Cr, 23.0 to 27.0% of Ni, 0.5 to 6.0% of Si, 1.2 to 1.6% of Mn, 1.2 to 1.4% of Mo, 0.8 to 1.4% of Ti, 0.10 to 0.15% of Al, C<0.01％，O<0.005％，N<0.005％，P<0.01％，S<0.01 percent, and the balance being iron. The preparation method of the austenitic aged stainless steel comprises the following steps: batching → pure smelting → casting molding → forging and hot rolling → multistage aging heat treatment. According to the invention, a certain content of titanium and aluminum are added into steel, and the multi-stage aging heat treatment process with different temperatures is adopted to promote Ni with different sizes3The precipitation of Ti precipitated phase improves the strength of an austenite matrix, the content of impurities in steel is controlled by adopting a pure smelting process, and the corrosion performance of the matrix in an oxidation-resistant medium nitric acid is improved by optimizing the content of silicon on the premise of ensuring that a complete austenite matrix is obtained, so that the optimal matching of the material strength and the corrosion resistance is obtained.
Description
Technical Field
The invention relates to high-strength austenitic aging stainless steel resistant to concentrated nitric acid corrosion of oxidizing ions and a preparation method thereof, belonging to the technical field of materials.
Background
Nuclear power is gaining increasing acceptance as a safe, clean, reliable and low-carbon source that can replace fossil fuels on a large scale. Nuclear energy is an environment-friendly energy source, the development of the nuclear energy can solve the energy problem on one hand, but nuclear waste generated by a nuclear power station generates inevitable pollution to the environment, and the post-treatment problem of the nuclear waste, namely spent fuel, is a worldwide problem in the nuclear energy development country all the time and also restricts the sustainable development of nuclear power.
Compared with the early mature commercial spent fuel batch dissolver, the rotary wheel type continuous spent fuel dissolver is favored due to a series of advantages of high efficiency, strong processing capacity and the like, reaches the level of commercial application, and the nuclear energy-enhanced national france successfully establishes the only continuous spent fuel dissolver which is put into industrial operation in the world. The research of China is started from 2010, the research of a scientific research prototype is planned to be completed in 2021, and the research provides technical support for a large-scale commercial nuclear fuel post-processing plant with the processing capacity of 800 tons in 2025 years. The structure of the rotary wheel type continuous spent fuel dissolver can be divided into two parts: one part is a groove body for containing concentrated nitric acid, and the other part is a complete set of actuating mechanism (large rotating wheel and other mechanisms) for operating the short section of the spent fuel. The large rotating wheel adopts a structural form of a face gear, and forms a face gear transmission mode with a small gear on the top cover to drive the large rotating wheel to rotate.
The service condition of a large runner which is a core component of the runner type continuous spent fuel dissolver is extremely harsh, and on one hand, the spent fuel contains Cr with certain concentration6+The oxidizing ions can aggravate the corrosion of the concentrated nitric acid, and on the other hand, the large runner needs to bear continuous abrasion caused by the rotation of the gear, so that the material is required to have not only the corrosion resistance in the concentrated nitric acid of the oxidizing ions, but also certain hardness, and the current commercial austenitic stainless steel cannot achieve both high strength and nitric acid corrosion resistance. The service life of austenitic stainless steel adopted by a large runner of a commercial continuous spent fuel processor successfully in France in a nuclear power strong country is as long as 20 years, while the service life of a material of the large runner in the current test stage of China is less than 1 month, and the performance difference of key core component materials is very different. Therefore, the development of the high-strength austenitic stainless steel with resistance to the corrosion of the concentrated nitric acid containing the oxidizing ions for the continuous spent fuel dissolver 'large wheel' is urgently needed.
Disclosure of Invention
The invention aims to provide high-strength austenitic aging stainless steel resistant to concentrated nitric acid corrosion containing oxidative ions and a preparation method thereof3The Ti phase content improves the strength and hardness of an austenite matrix; secondly, under the precondition of ensuring that a complete austenite matrix is obtained, a layer of protective silicate oxidation is generated on the surface of the steel by optimizing the silicon content in the alloyThe corrosion resistance of the matrix in an oxidizing ion concentrated nitric acid medium is improved; thirdly, an ultra-low carbon purification smelting technology is adopted, the corrosion resistance of the steel is improved by reducing the number of corrosion-prone carbides on grain boundaries and the content of impurities in the steel, the technical difficulty that the strength and the corrosion resistance of the austenitic stainless steel are both considered is solved, and the material with high hardness, high strength and excellent corrosion resistance is obtained.
The technical scheme of the invention is as follows:
a high-strength austenitic aged stainless steel resisting the corrosion of oxidizing ions and concentrated nitric acid comprises the following chemical components in percentage by weight: 16.0-20.0% of Cr, 23.0-27.0% of Ni, 0.5-6.0% of Si, 1.2-1.6% of Mn, 1.2-1.4% of Mo, 0.8-1.4% of Ti, 0.10-0.15% of Al, 0.01% of C, 0.005% of O, 0.005% of N, 0.01% of P, 0.01% of S and the balance of Fe.
The high-strength austenitic aged stainless steel resistant to corrosion by oxidizing ions concentrated nitric acid is characterized in that, preferably, the ratio of Si:3.5 to 4.5 percent.
The preparation method of the high-strength austenitic aged stainless steel resisting the corrosion of the oxidizing ion concentrated nitric acid comprises the following steps:
(1) mixing the chemical components in proportion, and obtaining steel ingots through purification smelting and pouring;
(2) forging the obtained steel ingot in an austenite phase region;
(3) hot rolling the forged steel ingot: the rolling temperature is 1150-1200 ℃, the reduction amount of each pass of rolling is controlled to be 10-15%, the total reduction amount is controlled to be 60-80%, and the hot rolling is carried out and then the air cooling is carried out to the room temperature;
(4) and carrying out heat treatment after hot rolling.
The preparation method of the high-strength austenitic aged stainless steel with the resistance to the corrosion of the oxidizing ion concentrated nitric acid comprises the following steps of (2): the initial forging temperature is 1150-1200 ℃, the forging ratio is more than 8, and the forging is carried out by air cooling to the room temperature.
The preparation method of the high-strength austenitic aged stainless steel with the resistance to the corrosion of the oxygen-containing ionic concentrated nitric acid comprises the following heat treatment process in step (4): firstly, keeping the temperature of 980 +/-20 ℃ for 60min +/-10 min, then carrying out water quenching to the room temperature, keeping the temperature of 735 +/-10 ℃ for 16h +/-1 h, then air-cooling to the room temperature, then keeping the temperature of 695 +/-10 ℃ for 16h +/-1 h, then air-cooling to the room temperature, finally keeping the temperature of 650 +/-10 ℃ for 16h +/-1 h, and then air-cooling to the room temperature.
The preparation method of the high-strength austenitic aged stainless steel resisting the corrosion of the oxidizing ion concentrated nitric acid comprises the steps of carrying out heat treatment on the high-strength austenitic stainless steel resisting the corrosion of the oxidizing ion concentrated nitric acid, wherein the HRC hardness reaches more than 30, and the high-strength austenitic aged stainless steel contains 7g/L Cr at 95 DEG C6+And a corrosion rate of less than 0.30mm/year in a nitric acid environment of 1.7g/L V oxidizing ions at 6 mol/L.
The design concept of the invention has three points, as follows:
1) and (3) a multi-stage aging heat treatment system corresponding to precipitation of precipitated phases with different sizes and quantities: ti with the mass fraction of 0.8-1.4% is added into austenitic steel, and an aging heat treatment system is adopted to promote the matrix to separate out the coherent gamma' phase Ni3Ti greatly improves the hardness and the strength of the material matrix. Since the size of the gamma' phase is closely related to the ageing treatment temperature and time, the optimum ageing heat treatment regime for the steel of the invention was determined by orthogonal tests: namely, the steel is subjected to heat preservation at 735 +/-10 ℃ for 16h +/-1 h, then air-cooled to room temperature, then subjected to heat preservation at 695 +/-10 ℃ for 16h +/-1 h, then air-cooled to room temperature, and finally subjected to heat preservation at 650 +/-10 ℃ for 16h +/-1 h, and then air-cooled to room temperature, and by adopting the heat treatment system, the uniform dispersion distribution of gamma' phases with different sizes and quantities in a matrix is promoted, and the HRC hardness of the steel reaches more than 30.
2) The Si content in the steel is optimized as follows: the steel of the invention can be added with a certain content of Si to form silicate to cover the surface of the material, thereby inhibiting the further occurrence of nitric acid corrosion and effectively improving the nitric acid corrosion resistance of the steel of the invention. On one hand, the Si content in the steel is low, and the corrosion resistance can not be ensured, on the other hand, if the Si content in the steel is high, the generation of a high-temperature ferrite phase is easy to cause, the comprehensive performances of the high-temperature ferrite phase, such as mechanics, corrosion and the like are deteriorated, and the optimal range of the Si content in the steel is obtained through experiments: 3.5 to 4.5 wt%.
3) The ultra-low carbon purification smelting technology comprises the following steps: the addition of a certain amount of C in the steel is easy to form carbide on the grain boundary of Cr in the steel, so that the content of Cr dissolved in the steel is reduced, a local micro-battery is formed on the grain boundary, and the corrosion resistance of the material is greatly reduced. The invention provides the component design idea of ultra-low carbon purification, reduces the carbide precipitation of Cr on the grain boundary in the heat treatment process, improves the corrosion resistance of the grain boundary, strictly controls the content of harmful elements such as P, S and O in steel by adopting a purification smelting technology, reduces the content of harmful phases such as inclusion and the like which are easy to cause pitting corrosion on the grain boundary in the steel, and further improves the corrosion resistance of the material.
The invention has the advantages and beneficial effects that:
according to the invention, a certain content of Ti element is added into austenitic stainless steel and a multi-stage aging heat treatment process is adopted, so that the uniform dispersion distribution of gamma' phase in the austenitic stainless steel is realized, and Ni with different sizes is promoted3The precipitation of Ti precipitated phase ensures the strength of the austenite matrix of the steel. On the other hand, on the premise of ensuring a single austenite structure, the Si content in the steel is optimized, so that a continuous and compact protective silicate oxide film is formed on the surface of the steel, the corrosion resistance of the steel in oxidizing ion concentrated nitric acid is improved, and the optimal matching of material strength and corrosion resistance is obtained. Finally, a low-carbon pure smelting technology is adopted, the contents of Cr carbide and impurities in the steel are controlled, the grain boundary stability and the corrosion resistance of the steel are improved, the technical barrier that the strength and the high-temperature concentrated nitric acid corrosion resistance of austenitic stainless steel cannot be considered at the same time is solved, and the high-strength austenitic aging stainless steel with excellent oxidation-resistant ion concentrated nitric acid corrosion resistance is obtained.
Drawings
FIG. 1 is a schematic view of a homogenized metallographic structure in example 1.
FIG. 2 is a schematic representation of the TEM structure after the multistage aging heat treatment of example 1.
FIG. 3 shows that example 1 contains 7g/L of Cr at 95 ℃6+And the corrosion morphology is shown in the figure after the etching is carried out for 180 hours in a nitric acid environment with oxidizing ions of 6mol/L at 1.7g/L V.
FIG. 4 shows comparative example 1 containing 7g/L of Cr at 95 ℃6+And the corrosion morphology is shown in the figure after the etching is carried out for 180 hours in a nitric acid environment with oxidizing ions of 6mol/L at 1.7g/L V.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto. The steel in the embodiment and the steel in the comparative example are subjected to pure smelting, forging, hot rolling and heat treatment, then processed into a hardness test sample and a corrosion test sample, and finally tested for the hardness and the time of 180 hours, wherein the oxidation ions are contained in the concentrated nitric acid corrosion performance.
In the specific implementation process, a certain content of titanium element is added into the steel, and the uniform dispersion distribution of the gamma' phase is promoted by adopting the multistage aging heat treatment, so that the matrix strength of the steel is ensured. Under the precondition of ensuring a single austenite structure, the Si content in the steel is optimized, and the corrosion resistance of the steel in the oxidizing ion concentrated nitric acid is improved. The impurity content in the steel is controlled by adopting a pure smelting process, the corrosion resistance of a matrix crystal boundary is improved, and the best matching of the material strength and the corrosion resistance is obtained. The preparation process of the high-strength austenitic aged stainless steel with the resistance to the corrosion of the concentrated nitric acid containing the oxidizing ions comprises the following steps: the preparation method comprises the following steps of burdening → pure smelting → casting molding → forging and hot rolling → three-stage aging heat treatment, and the preparation method of the embodiment 1-5 comprises the following steps:
(1) mixing the chemical components in proportion, and obtaining a steel ingot through pure smelting and pouring;
(2) the ingot obtained is forged in the austenite phase region: the primary forging temperature is 1150-1200 ℃ (1153 ℃, 1164 ℃, 1198 ℃, 1182 ℃ and 1176 ℃ in the examples 1-5), the forging ratio is more than 8 (8.4, 8.1, 9.2, 8.6 and 8.3 in the examples 1-5), and the forging is carried out and then air cooling is carried out to the room temperature;
(3) hot rolling the forged steel ingot: the rolling temperature is 1150-1200 ℃ (1153 ℃, 1185 ℃, 1156 ℃, 1197 ℃ and 1188 ℃ in examples 1-5), the reduction amount of each pass of rolling is controlled to be 10-15% (10.5%, 12.7%, 11.5%, 14.9% and 13.8% in examples 1-5), the total reduction amount is controlled to be 60-80% (60.8%, 70.4%, 75.2%, 79.6% and 65.3% in examples 1-5), and the hot rolling is carried out and then the air cooling is carried out to the room temperature;
(4) carrying out three-stage aging heat treatment after hot rolling: firstly, keeping the temperature of 980 ℃ +/-20 ℃ (981 ℃, 963 ℃, 991 ℃, 986 ℃ and 971 ℃) for 60min +/-10 min (60 min, 51min, 56min, 69min and 64min in examples 1 to 5), then carrying out water quenching to the room temperature, keeping the temperature of 735 ℃ +/-10 ℃ (734 ℃, 744 ℃, 726 ℃, 740 ℃ and 731 ℃) for 16h +/-1 h (16.0 h, 16.9h, 15.2h, 16.4h and 15.8h in examples 1 to 5) and then air cooling to the room temperature; then, keeping the temperature at 695 +/-10 ℃ (695 ℃, 704 ℃, 687 ℃, 701 ℃ and 692 ℃ respectively in the embodiments 1-5) for 16 +/-1 h (16.0 h, 16.8h, 15.1h, 16.5h and 15.6h respectively in the embodiments 1-5), and then air-cooling to the room temperature; finally, the temperature is maintained at 650 +/-10 ℃ (650 ℃, 659 ℃, 642 ℃, 654 ℃ and 646 ℃ in examples 1 to 5) for 16h +/-1 h (16.0 h, 16.7h, 15.3h, 16.2h and 15.7h in examples 1 to 5), and then the air is cooled to the room temperature.
The invention is explained in more detail below with reference to the figures and examples.
Example 1
In this example, the chemical components of the high strength austenitic aged stainless steel resistant to corrosion by concentrated nitric acid containing oxidizing ions are as follows by weight percent: 17.62 percent of Cr, 24.75 percent of Ni, 3.90 percent of Si, 1.47 percent of Mn, 1.28 percent of Mo, 1.18 percent of Ti, 0.11 percent of Al, 0.0043 percent of C, 0.0027 percent of O, 0.0032 percent of N, 0.0074 percent of P, 0.0045 percent of S and the balance of iron.
Example 2
In this example, the chemical components of the high strength austenitic aged stainless steel resistant to corrosion by concentrated nitric acid containing oxidizing ions are as follows by weight percent: 19.86% of Cr, 26.93% of Ni, 4.45% of Si, 1.58% of Mn, 1.37% of Mo, 1.38% of Ti, 0.15% of Al, 0.0089% of C, 0.0019% of O, 0.0046% of N, 0.0084% of P, 0.0040% of S and the balance of iron.
Example 3
In this example, the chemical components of the high strength austenitic aged stainless steel resistant to corrosion by concentrated nitric acid containing oxidizing ions are as follows by weight percent: 16.14 percent of Cr, 23.18 percent of Ni, 3.52 percent of Si, 1.23 percent of Mn, 1.21 percent of Mo, 0.82 percent of Ti, 0.10 percent of Al, 0.0068 percent of C, 0.0032 percent of O, 0.0042 percent of N, 0.0061 percent of P, 0.0038 percent of S and the balance of iron.
Example 4
In this example, the chemical components of the high strength austenitic aged stainless steel resistant to corrosion by concentrated nitric acid containing oxidizing ions are as follows by weight percent: 18.95% of Cr, 26.08% of Ni, 4.27% of Si, 1.51% of Mn, 1.36% of Mo, 1.26% of Ti, 0.13% of Al, 0.0049% of C, 0.0024% of O, 0.0029% of N, 0.0074% of P, 0.0067% of S and the balance of iron.
Example 5
In this example, the chemical components of the high strength austenitic aged stainless steel resistant to corrosion by concentrated nitric acid containing oxidizing ions are as follows by weight percent: 17.14 percent of Cr, 23.97 percent of Ni, 3.78 percent of Si, 1.32 percent of Mn, 1.25 percent of Mo, 0.97 percent of Ti, 0.11 percent of Al, 0.0038 percent of C, 0.0037 percent of O, 0.0025 percent of N, 0.0052 percent of P, 0.0028 percent of S and the balance of iron.
Comparative example 1
In this comparative example, the chemical composition of the high-strength austenitic aged stainless steel resistant to corrosion by oxidizing ions concentrated nitric acid was not added with Si element, and the other chemical compositions were the same as in example 1, and the smelting method, hot working (forging and hot rolling), and aging heat treatment processes were the same as in examples 1 to 5.
As shown in Table 1, in comparison with example 1, it is found that in comparative example 1, since Si is not added to a certain amount, the HRC hardness is less than 30 because of no solid solution strengthening of Si, and the resistance to the corrosion by concentrated nitric acid containing oxidizing ions is remarkably lowered.
Comparative example 2
In this comparative example, the chemical composition, the smelting method and the hot working (forging and hot rolling) of the high strength austenitic aged stainless steel resistant to the corrosion by oxidizing ion concentrated nitric acid were exactly the same as those of example 2, but the aging heat treatment was not performed, and the corrosion resistance by oxidizing ion concentrated nitric acid was comparable to that of example 2, but the HRC hardness was lower than 30.
Comparative example 3
In this comparative example, the chemical composition, smelting method and hot working (forging and hot rolling) of the high strength austenitic aged stainless steel resistant to corrosion by oxidizing ion concentrated nitric acid were exactly the same as in example 2, and only the primary aging heat treatment was performed: after the temperature is kept at 736 ℃ for 16.0h, the mixture is cooled to room temperature by air, the performance of resisting the corrosion of the concentrated nitric acid containing oxidative ions is equivalent to that of example 2, but the HRC hardness is lower than 30.
Comparative example 4
In this comparative example, the chemical composition, smelting method and hot working (forging and hot rolling) of the high strength austenitic aged stainless steel resistant to corrosion by oxidizing ion concentrated nitric acid were exactly the same as in example 2, and a secondary aging heat treatment was performed: the temperature is kept at 736 ℃ for 16.0h, then air-cooled to room temperature, and then kept at 695 ℃ for 16.1h, then air-cooled to room temperature, and the oxygen-containing ion concentrated nitric acid corrosion resistance is equivalent to that of example 2, but the HRC hardness is lower than 30.
HRC hardness and content of 7g/LCr at 95 ℃ of examples and comparative examples6+And a corrosion rate in a nitric acid environment of 1.7g/LV oxidizing ions of 6mol/L are shown in Table 1.
TABLE 1
As can be seen from Table 1, the invention promotes coherent gamma' -phase Ni by adding a certain content of Ti and adopting three-stage aging heat treatment3Ti is dispersed and separated out evenly in the matrix, and the HRC hardness of the steel can reach more than 30. On the premise of ensuring that the matrix is single austenite, the Si content is optimized, the corrosion performance of the steel in a concentrated nitric acid corrosion medium containing oxidizing ions is greatly improved, and the corrosion rate is 0.30mmAnd/year or less. By adopting an ultra-low carbon purification smelting technology, the content of C in the steel is controlled to be below 100ppm, the precipitation of Cr carbide is reduced, the content of harmful impurity elements such as P and S is controlled, the carbide and inclusion which are easy to generate pitting corrosion are not formed on a matrix grain boundary, and the nitric acid corrosion resistance of the steel in the concentrated nitric acid containing oxidizing ions is further improved.
As shown in FIG. 1, as can be seen from the schematic view of the metallographic microstructure after royal water etching in example 1 of the present invention, the structure of the steel was a fully austenitic structure, and the average grain size of the steel of the present invention was as small as 20.7 μm because of the normalizing water-cooling heat treatment at a maximum temperature of not more than 1000 ℃.
As shown in FIG. 2, it can be seen from the schematic diagram of the transmission structure in example 1 of the present invention that there are no harmful phases such as carbides and inclusions at the grain boundaries of austenitic steel, and a large amount of gamma prime Ni phases having different sizes and dispersed distributions are present3Ti, the size of precipitated phase is less than 100 nm.
As shown in FIG. 3, the alloy obtained in example 1 of the present invention contains 7g/L of Cr at 95 ℃6+And the corrosion morphology after 180 hours of corrosion in a nitric acid environment with oxidizing ions of 6mol/L of 1.7g/L V shows that no obvious corrosion product is seen on the surface, no grain boundary corrosion occurs, and the excellent corrosion resistance is shown.
As shown in FIG. 4, comparative example 1 of the present invention contains 7g/L of Cr at 95 ℃6+And the corrosion morphology of the material after being corroded for 180 hours in a nitric acid environment with oxidizing ions of 6mol/L of 1.7g/L V shows that the material has obvious grain boundary corrosion, has a plurality of large-size pitting pits in the crystal and shows poor corrosion resistance.
The example results show that the invention promotes different sizes of coherent gamma' -phase Ni by adding certain contents of titanium and aluminum in the steel of the invention and adopting the multistage aging heat treatment process with different temperatures3Ti is dispersed and precipitated in the matrix uniformly, so that the hardness of the matrix is ensured; by optimizing the Si content in the steel, the corrosion resistance of the steel in the concentrated nitric acid containing the oxidative ions is greatly improved; in addition, the carbide and the clamp on the steel grain boundary of the invention are purified by adopting an ultra-low carbon purification smelting technologyThe content of impurities is further improved, the concentrated nitric acid corrosion resistance is further improved, and the technical problem of both the strength and the corrosion resistance of the austenitic stainless steel is solved. After the multi-stage aging heat treatment, the HRC hardness of the high-strength austenitic stainless steel reaches more than 30 (preferably 31.4-33.6), and the high-strength austenitic stainless steel resists the temperature of 95 ℃ and contains 7g/L Cr6+And a nitric acid etch rate of less than 0.30mm/year for an oxidizing ion of 6mol/L at 1.7g/L V.
Claims (6)
1. The high-strength austenitic aged stainless steel resistant to the corrosion of the concentrated nitric acid containing the oxidizing ions is characterized by comprising the following chemical components in percentage by weight: 16.0-20.0% of Cr, 23.0-27.0% of Ni, 0.5-6.0% of Si, 1.2-1.6% of Mn, 1.2-1.4% of Mo, 0.8-1.4% of Ti, 0.10-0.15% of Al, 0.01% of C, 0.005% of O, 0.005% of N, 0.01% of P, 0.01% of S and the balance of Fe.
2. High strength austenitic aged stainless steel with resistance to corrosion by concentrated nitric acid containing oxidizing ions according to claim 1, characterized in that, preferably, the ratio of Si:3.5 to 4.5 percent.
3. A method for preparing a high strength austenitic aged stainless steel resistant to concentrated nitric acid corrosion containing oxidizing ions according to any of claims 1-2, characterized by comprising the steps of:
(1) mixing the chemical components in proportion, and obtaining steel ingots through purification smelting and pouring;
(2) forging the obtained steel ingot in an austenite phase region;
(3) hot rolling the forged steel ingot: the rolling temperature is 1150-1200 ℃, the reduction amount of each pass of rolling is controlled to be 10-15%, the total reduction amount is controlled to be 60-80%, and the hot rolling is carried out and then the air cooling is carried out to the room temperature;
(4) and carrying out heat treatment after hot rolling.
4. A method of producing a high strength austenitic aged stainless steel with resistance to concentrated nitric acid corrosion containing oxidizing ions according to claim 3, wherein in step (2), the forging process is: the initial forging temperature is 1150-1200 ℃, the forging ratio is more than 8, and the forging is carried out by air cooling to the room temperature.
5. A method of producing a high strength austenitic aged stainless steel with resistance to concentrated nitric acid corrosion containing oxidizing ions according to claim 3, characterized in that, in the step (4), the heat treatment process is: firstly, keeping the temperature of 980 +/-20 ℃ for 60min +/-10 min, then carrying out water quenching to the room temperature, keeping the temperature of 735 +/-10 ℃ for 16h +/-1 h, then air-cooling to the room temperature, then keeping the temperature of 695 +/-10 ℃ for 16h +/-1 h, then air-cooling to the room temperature, finally keeping the temperature of 650 +/-10 ℃ for 16h +/-1 h, and then air-cooling to the room temperature.
6. A method of producing a high strength austenitic aged stainless steel having resistance to corrosion by concentrated nitric acid containing oxidizing ions according to claim 5, characterized in that the high strength austenitic stainless steel having resistance to corrosion by concentrated nitric acid containing oxidizing ions after heat treatment has an HRC hardness of 30 or more and contains 7g/L Cr at 95 ℃6+And a corrosion rate of less than 0.30mm/year in a nitric acid environment of 1.7g/L V oxidizing ions at 6 mol/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116024504A (en) * | 2022-12-16 | 2023-04-28 | 坤石容器制造有限公司 | Ferrite stainless steel for high-purity unstable electron special gas in semiconductor industry and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB812582A (en) * | 1956-07-18 | 1959-04-29 | Universal Cyclops Steel Corp | Ferrous base alloys |
| US5021215A (en) * | 1989-01-30 | 1991-06-04 | Sumitomo Metal Industries, Ltd. | High-strength, heat-resistant steel with improved formability and method thereof |
| US5244513A (en) * | 1991-03-29 | 1993-09-14 | Mitsubishi Jukogyo Kabushiki Kaisha | Fe-cr-ni-si shape memory alloys with excellent stress corrosion cracking resistance |
| CN101194037A (en) * | 2005-04-11 | 2008-06-04 | 住友金属工业株式会社 | Austenitic stainless steel |
| CN102031461A (en) * | 2010-10-22 | 2011-04-27 | 重庆仪表材料研究所 | Heat-resisting alloy with high yield ratio, high toughness and long-run elasticity stability |
| CN103173698A (en) * | 2013-04-09 | 2013-06-26 | 北京科技大学 | Dispersed precipitated phase strengthened austenitic stainless steel with high Cr and high Ni and thermal processing method |
| CN104032233A (en) * | 2014-05-27 | 2014-09-10 | 中国核动力研究设计院 | Austenite stainless steel and a manufacturing technology thereof |
| CN106544601A (en) * | 2016-12-29 | 2017-03-29 | 董世祥 | Many performance high temperature resistant series cast steels |
| CN107406945A (en) * | 2015-03-26 | 2017-11-28 | 新日铁住金不锈钢株式会社 | The excellent stainless steel of soldering |
| CN109930067A (en) * | 2019-03-20 | 2019-06-25 | 太原钢铁(集团)有限公司 | Heat-proof corrosion-resistant austenitic stainless steel and preparation method thereof |
| JP2020104145A (en) * | 2018-12-27 | 2020-07-09 | ヤマコー株式会社 | Method for molding high-silicon stainless steel |
-
2021
- 2021-02-07 CN CN202110182515.8A patent/CN113061802B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB812582A (en) * | 1956-07-18 | 1959-04-29 | Universal Cyclops Steel Corp | Ferrous base alloys |
| US5021215A (en) * | 1989-01-30 | 1991-06-04 | Sumitomo Metal Industries, Ltd. | High-strength, heat-resistant steel with improved formability and method thereof |
| US5244513A (en) * | 1991-03-29 | 1993-09-14 | Mitsubishi Jukogyo Kabushiki Kaisha | Fe-cr-ni-si shape memory alloys with excellent stress corrosion cracking resistance |
| CN101194037A (en) * | 2005-04-11 | 2008-06-04 | 住友金属工业株式会社 | Austenitic stainless steel |
| CN102031461A (en) * | 2010-10-22 | 2011-04-27 | 重庆仪表材料研究所 | Heat-resisting alloy with high yield ratio, high toughness and long-run elasticity stability |
| CN103173698A (en) * | 2013-04-09 | 2013-06-26 | 北京科技大学 | Dispersed precipitated phase strengthened austenitic stainless steel with high Cr and high Ni and thermal processing method |
| CN104032233A (en) * | 2014-05-27 | 2014-09-10 | 中国核动力研究设计院 | Austenite stainless steel and a manufacturing technology thereof |
| CN107406945A (en) * | 2015-03-26 | 2017-11-28 | 新日铁住金不锈钢株式会社 | The excellent stainless steel of soldering |
| CN106544601A (en) * | 2016-12-29 | 2017-03-29 | 董世祥 | Many performance high temperature resistant series cast steels |
| JP2020104145A (en) * | 2018-12-27 | 2020-07-09 | ヤマコー株式会社 | Method for molding high-silicon stainless steel |
| CN109930067A (en) * | 2019-03-20 | 2019-06-25 | 太原钢铁(集团)有限公司 | Heat-proof corrosion-resistant austenitic stainless steel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 田家龙等: "多相强化型马氏体时效不锈钢中的合金元素偏聚效应", 《金属学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116024504A (en) * | 2022-12-16 | 2023-04-28 | 坤石容器制造有限公司 | Ferrite stainless steel for high-purity unstable electron special gas in semiconductor industry and preparation method thereof |
| CN116024504B (en) * | 2022-12-16 | 2024-08-02 | 坤石容器制造有限公司 | Ferrite stainless steel for high-purity unstable electron special gas in semiconductor industry and preparation method thereof |
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