CN115874103A - High-strength austenitic stainless steel for ultra-pure electronic special gas in semiconductor industry and preparation method thereof - Google Patents
High-strength austenitic stainless steel for ultra-pure electronic special gas in semiconductor industry and preparation method thereof Download PDFInfo
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Abstract
The invention relates to high-strength austenitic stainless steel for ultra-pure electronic special gas in the semiconductor industry and a preparation method thereof, belonging to the technical field of materials. The austenitic stainless steel comprises the following chemical components in percentage by weight: 24.0 to 30.0 percent of Cr, 25.0 to 40.0 percent of Ni, 4.0 to 8.0 percent of Mo, 0 to 3.0 percent of W, 0.1 to 1.0 percent of N, 0 to 0.01 percent of Se, 0.3 percent of Si, 0.01 percent of C, 0.05 percent of Mn, 0.01 percent of Al, 0.005 percent of P, 0.001 percent of S, 0.004 percent of O and the balance of iron. The preparation method of the austenitic stainless steel comprises the following steps: batching → pure smelting → casting molding → forging and hot rolling → heat treatment → cold working. The invention adopts the design idea of ultra-low carbon and low manganese components, controls the chromium equivalent and the nickel equivalent and ensures that a complete austenite structure is obtained; adding a certain content of nitrogen element, adopting homogenization heat treatment to promote solid solution of the nitrogen element, and finally improving the strength of the matrix by adopting a cold rolling mode; the pure smelting process is adopted to control the content of impurities in the steel, improve the corrosion resistance of the matrix grain boundary and obtain the best matching of the toughness and the corrosion resistance of the material.
Description
Technical Field
The invention relates to high-strength austenitic stainless steel for ultra-pure electronic special gas in the semiconductor industry and a preparation method thereof, belonging to the technical field of materials.
Background
The gas is blood for industrial economic development, covers various fields of social production and drives the development of scientific technology. Electronic gases refer to gases used in the production of semiconductors and other electronic products. Compared with the traditional industrial gas, the electronic gas has extremely high requirement on the purity of the gas, so the electronic gas is also called as the electronic special gas. Ultra-pure electronic special gas (volume purity reaches 6 and 9, namely 99.9999 percent) used in the semiconductor industry is a key factor for promoting the progress of the semiconductor industry. The ultra-pure electronic special gas is one of the weakest links in the domestic high-end electrochemical process chain as the upstream of the semiconductor industry chain and the like from the current domestic industrial development situation, so that the independent development of the Chinese electronic gas plays a vital role in the development of the semiconductor chip industry in China and is directly related to the national economic development and the national strategic safety.
At present, the utilization rate of ultra-pure electronic special gas in the domestic high-end semiconductor manufacturing industry chain is less than 15%, the localization rate of the electronic grade special gas is lower, and the reason for the utilization rate is that three technical barriers exist in the purification and preparation of the electronic special gas: 1) the technical difficulty of deep purification is high, 2) the concept of component analysis and inspection of special electronic gas is backward, 3) packaging, storage and transportation cannot keep pace, and production and application of ultra-pure gas require high-quality gas packaging, storage and transportation containers. Since the introduction of the special gas into the Chinese market in the middle of the 80 th year in the 20 th century, the electronic special gas industry in China has been developed and precipitated for 40 years, and with the continuous experience accumulation and technical progress of domestic enterprises in the first two technical barriers of electronic special gas, namely, the aspects of electronic special gas purification and component detection, advanced enterprises in China have realized breakthrough on partial products, reach international traffic standards, gradually realize import substitution, and the localization of the special gas has objective conditions. However, no progress has been made in the key materials such as gas cylinders and delivery pipelines used for packaging, storage and transportation of electronic special gas, especially in the key processes such as preparation of high-strength austenitic stainless steel used for ultra-pure electronic special gas, and the key equipment faces serious patent technology blockages. Therefore, if the domestic substitution of industrial matching links including materials and equipment can not be realized early, the sustainable development of the semiconductor industry in China is limited.
At present, international advanced semiconductor countries all establish and establish corresponding national/semiconductor standards, and Japan develops KS series materials by adopting a special preparation process according to the properties of electronic special gases, thereby supporting the high-speed development of the semiconductor industry. The United states establishes a strict internal control standard process aiming at raw materials and subsequent process flows, and guarantees the leadership of the semiconductor industry. Korea has developed a series of special treatment processes for the surface of the material according to the properties of the transport gas, ensuring the steady development of its semiconductor industry. Compared with foreign gas companies, most domestic gas companies still have single supply products, the material used by the semiconductor storage container is basically 316L austenitic stainless steel, the yield strength and the tensile strength are low, and because of high alloy elements such as carbon, manganese and the like in the 316L austenitic stainless steel, a large amount of dust is generated in a welding process of a gas pipeline of the material, great trouble is brought to cleaning of the inner wall of the gas pipeline, the short plates of the material cannot meet the development requirements of the semiconductor industry in China, and particularly the storage and transportation container and the corresponding gas transportation pipeline which are required by ultra-pure electronic special gas used in the high-end semiconductor field and have certain pressure are used. The material of the pressure container material and the surface treatment process used by the existing electronic special gas in China fall behind, the whole technology does not conform to the international standard, and a corresponding material and process standard system between the material selection of the ultra-pure electronic special gas and the gas cylinder, the surface treatment of the inner wall and the like is not established. Therefore, in order to promote the development of the semiconductor industry and promote the localization of ultra-pure electronic special gas, china also successively releases instructional documents, and aims to promote the localization of key materials including special gas and get rid of the situation that the key materials are restricted by people. Under the influence of multiple factors such as technical progress, demand pull, policy stimulation and the like, the research and development of key materials such as high-strength austenitic stainless steel and the like used for ultra-pure electronic special gas in the semiconductor industry are imperative, and the research and development are related to the steady continuous forward development of the semiconductor industry in China and are directly related to the national economic development and the national strategic safety.
Disclosure of Invention
The invention aims to provide high-strength austenitic stainless steel for ultra-pure electronic special gas in the semiconductor industry and a preparation method thereof, firstly, the design idea of ultra-low carbon and low manganese alloy components is adopted, and on one hand, the corrosion performance of the austenitic stainless steel can be improved by reducing the precipitation of chromium carbide on a grain boundary; on the other hand, the surface smoothness of the material after electrolytic polishing can be improved, and the requirement of no dust during material welding can be met. The second method is to add a certain amount of nitrogen element into the material by a special smelting method, and to adopt homogenization heat treatment before cold rolling to promote the N in the steel to be completely dissolved into the steel matrix, and to adopt cold deformation to improve the strength of the austenitic stainless steel matrix. In addition, by adding a proper amount of nitrogen content and controlling the chromium equivalent and the nickel equivalent by cold working, the complete austenite structure is ensured to be obtained, and the strengthening effect of solid solution nitrogen is fully exerted by cold working, so that the strength and the hardness of the austenite matrix are improved.
The technical scheme of the invention is as follows:
the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry comprises the following chemical components in percentage by weight: 24.0 to 30.0 percent of Cr, 25.0 to 40.0 percent of Ni, 4.0 to 8.0 percent of Mo, 0 to 3.0 percent of W, 0.1 to 1.0 percent of N, 0 to 0.01 percent of Se, less than 0.3 percent of Si, less than 0.01 percent of C, less than 0.05 percent of Mn, less than 0.01 percent of Al, less than 0.005 percent of P, less than 0.001 percent of S, less than 0.004 percent of O, and the balance of iron.
The high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry is preferably selected from N:0.4 to 0.8 percent.
The high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry is preferably 0.002-0.004% of Se.
The preparation method of the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry comprises the following steps:
(1) Mixing the chemical components in proportion, and obtaining steel ingots through purification smelting and casting;
(2) Forging the obtained steel ingot in an austenite phase region;
(3) Hot rolling the forged steel ingot: the rolling temperature is 1000-1100 ℃, 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) Carrying out heat treatment after hot rolling;
(5) And cold rolling the heat-treated plate.
The preparation method of the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry comprises the following steps of (2) forging: the forging temperature is 1000-1100 ℃, the forging ratio is more than 6.0, and the forging is carried out by air cooling to the room temperature.
The preparation method of the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry comprises the following heat treatment processes in the step (4): keeping the temperature at 1150-1200 ℃ for 30-60 min, and then carrying out oil cooling to room temperature.
The preparation method of the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry comprises the following steps of (5): the reduction of each pass is less than 15 percent, and the total reduction is controlled to be 40 to 60 percent.
The preparation method of the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry is characterized in that the yield strength of the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry after cold rolling is larger than 650MPa, the tensile strength is larger than 1000MPa, and the elongation is larger than 40%.
The content ranges of the main elements in the invention are explained as follows:
cr: chromium is an important element in high-chromium stainless steel and is the primary element determining the corrosion resistance of stainless steel because chromium increases the corrosion resistance of the steel itself while allowing the steel to easily form a chromium oxide layer thereon, but the minimum corrosion resistance required for stainless steel cannot be obtained when the Cr content is less than 15%. On the other hand, if the Cr content exceeds 30%, intermetallic compounds are easily precipitated, resulting in deterioration of hot workability and mechanical properties. Therefore, the chromium content in the present invention is controlled as follows: 24.0 to 30.0 weight percent.
Ni: nickel is an important element for controlling the complete austenitic structure of austenitic stainless steel. In order to ensure the stability of the austenitic structure, when the Ni content is less than 20%, the austenitic structure is unstable, and on the other hand, when the Ni content is high, the influence of Ni tends to saturate beyond a certain content, and at the same time, the material cost gradually increases. In addition, the inventive material contains more than 4.0wt% of ferrite-forming element Mo. Therefore, in order to obtain a complete austenitic structure and economy, the Ni content is limited to a range of 25.0 to 40.0wt%.
Mo: the corrosion resistance of austenitic stainless steel can be obviously improved by adding a certain content of molybdenum, but the molybdenum is a ferrite forming element and has the capacity equivalent to that of chromium, and the excessive content of molybdenum promotes the formation of a high-temperature ferrite phase, so that the performance of the material is deteriorated. Therefore, molybdenum having an effect of improving corrosion resistance can be added within a range that does not impair other properties such as hot workability and weldability. Therefore, the content of molybdenum in the steel of the invention is controlled as follows: 4.0 to 8.0wt percent.
W: tungsten is a high-melting-point metal, has a similar effect to molybdenum in steel, can improve the hardenability of steel, effectively inhibit the growth of crystal grains and reduce the overheating sensitivity of materials. The low-carbon austenitic stainless steel mainly plays a role in solid solution strengthening, increases the strength of an austenite matrix, improves the toughness of the steel, prevents low-temperature tempering brittleness and improves the wear resistance. When the tungsten content is added to 5% or more at that time, large-sized tungsten inclusions are easily generated due to the high melting point of tungsten, thereby deteriorating the properties of the material. Therefore, the optimized tungsten content in the steel of the invention is controlled as follows: 0.5 to 2.9 weight percent.
N: nitrogen is a strong austenite forming element, and can enlarge the austenite phase region and reduce the ferrite phase region, thereby inhibiting the formation of high-temperature ferrite in steel. Because the austenitic stainless steel adopts the design idea of ultra-low carbon and low manganese components, under the condition of certain nickel content, in order to obtain the full austenitic structure, certain content of nitrogen is added into the steel grade, and the nickel equivalent and the chromium equivalent are balanced, thereby ensuring that the full austenitic structure is obtained. In addition, nitrogen can greatly improve the strength of the steel in the final cold working process, but chromium nitride is easily formed due to too high nitrogen content, so that the corrosion resistance of the steel is reduced. Therefore, the optimized nitrogen content in the steel of the invention is as follows: 0.4 to 0.8 weight percent of N.
Se: the rare earth has the functions of purifying molten steel, modifying and mixing impurities and microalloying, and is beneficial to improving the cold stamping formability and the corrosion resistance of steel. A certain amount of rare earth can obviously improve the plasticity and toughness of the material and improve the transverse performance and low-temperature toughness of steel. Further, selenium has an effect of improving arc stability in arc welding and an effect of suppressing the shape change of the molten metal. When the selenium content is less than 0.001%, the above effect cannot be obtained. On the other hand, when the selenium content exceeds 0.01%, large-sized rare earth inclusions are formed, thereby seriously deteriorating the properties of the material. Therefore, the optimized content of the rare earth Se in the steel is as follows: 0.002-0.004 wt% of Se.
Si: although silicon has the function of deoxidizing to purify steel, it can also form oxide inclusions, thereby affecting the electrolytic polishing effect of the material and causing the generation of welding dust. When the Si content exceeds 0.3%, inclusions become large, and the dust-free property under welding conditions is particularly affected. Therefore, it is necessary to reduce the Si content, and the Si content in the steel of the invention is optimally controlled as follows: si <0.3wt%.
C: the carbon and the chromium can be precipitated at the grain boundary or the welding seam in the welding process after the heat treatment 23 C 6 Type carbides, thereby reducing the corrosion resistance of the material, affecting its subsequent electropolishing effect, given that the steel of the present invention is used for highly corrosive gases. Therefore, by adopting the design concept of ultra-low carbon components, the content of C in the steel is optimally controlled as follows: c<0.01wt％。
Mn: although manganese has the same effect of deoxidizing to purify steel as silicon, due to the volatile property of manganese, a large amount of dust is easily generated in the welding process, and the manganese is the most harmful element in the dust-free property of the material. Particularly, when the Mn content exceeds 0.2%, the amount of dust generated during welding increases sharply. In addition, mn is easy to form MnS inclusions with S, mirror surface effect after electrolytic polishing is influenced, and the content of Mn element is strictly controlled by the steel provided by the invention aiming at the welding dust-free characteristic and the mirror surface polishing requirement of the material. Therefore, the content of Mn in the steel is optimally controlled as follows: mn <0.05wt%.
Al: aluminum has the function of deoxidizing the steel to purify it. Aluminum produces oxide inclusions and these oxide inclusions tend to grow. In addition, aluminum is more easily oxidized than other alloying elements, and particularly, in the welding of the material, aluminum oxide inclusions are generated in the case where the oxygen content on the surface of the material is extremely low, which is one of the causes of the generation of welding dust, and therefore, it is necessary to reduce the aluminum content for austenitic stainless steel. Therefore, the Al content of the steel is optimally controlled as follows: al <0.01wt%.
S and P: respectively, the main inclusion forming elements and the harmful elements in the steel. Sulphur and manganese tend to form manganese sulphide inclusions which affect the mirror surface effect after electropolishing, and in addition inclusions have a very adverse effect on the impact toughness and creep properties of the steel, while impairing the creep properties of the steel. The phosphorus sharply raises the ductile-brittle transition temperature of the steel, increasing the cold brittleness of the steel. Therefore, the content control of sulfur and phosphorus in the steel of the invention is very strict: s is less than 0.001wt% and P is less than 0.005wt%.
O: oxygen is a main element for producing oxide inclusions in steel, and therefore, in order to reduce the inclusions in steel and ensure the purity of steel, the oxygen content therein must be minimized. Furthermore, oxide inclusions tend to collect and grow at the weld during welding. In order to reduce the amount of dust particles during welding, the oxygen content of the steel is limited to a very low level in order not to adversely affect the dust-free properties of the material. Therefore, the oxygen content in the steel of the invention is controlled very strictly: o <0.004wt%.
The innovative design concept of the present invention is four points, as follows:
1) The design of the components of the ultra-low carbon low manganese alloy comprises the following steps: carbon and chromium are easy to form chromium carbide in the heat treatment process, on one hand, the corrosion resistance of the material is reduced due to the reduction of Cr dissolved in the material, on the other hand, the carbide is easy to peel off after the subsequent surface treatment, so that the surface roughness of the material is influenced, a part of gas still remains after the container or the conveying pipeline is cleaned, and the secondary pollution is caused. Manganese has two functions, namely, the vapor pressure of the first manganese is lower, so that dust is easily formed in the welding process, and the second manganese easily forms manganese sulfide inclusion with sulfur to influence the roughness of the surface of the material. The design idea of ultra-low carbon and low manganese alloy is adopted, the carbon content is controlled to be below 50ppm, and the sulfur content is controlled to be below 10ppm, so that the roughness requirement of the material after surface treatment is ensured. In addition, the carbon equivalent is reduced, so that the welding performance of the material is obviously improved, and the requirement of no dust in material welding is met.
2) Design concept of high nitrogen composition: there are two effects with the addition of 0.4 to 0.8wt.% N in the steel: firstly, the strong austenite stabilization effect of N element which is solid-dissolved in a matrix by the homogenization heat treatment is utilized to balance the high Cr equivalent brought by the design of high chromium (24.0-30.0 wt%) and high molybdenum (4.0-8.0 wt%) in the steel, avoid the occurrence of high-temperature ferrite which deteriorates the comprehensive performance of the material due to the design of the composition of the ultra-low carbon and low manganese alloy, reduce the Ni content in the steel on the premise of ensuring the obtainment of a complete austenite structure, and ensure the economy of the invented material. Secondly, N dissolved in austenite can reduce dislocation of close packing in steel, and the strength of an austenite matrix can be greatly improved in a cold working process by limiting dislocation movement containing interstitial radicals, so that the working efficiency can be improved by improving the gas pressure of a container or a conveying pipeline.
3) The rare earth purification smelting technology comprises the following steps: the Se rare earth purification smelting technology is adopted, the oxygen content in the steel is controlled to be below 40ppm, and the content of harmful elements such as Al, P, S, O and the like which are easy to form inclusions in the steel is strictly controlled, so that the content of the inclusions formed by the elements in the steel is reduced, the roughness of the material after surface treatment is ensured, and the secondary pollution of ultra-pure electronic special gas is avoided.
4) And (3) cold deformation process control: by controlling the cold deformation within 40-60%, the crystal grains of the matrix are refined, and a large amount of dislocation is introduced into the matrix by utilizing the work hardening of the solid-solution nitrogen element, so that the strength and the corrosion resistance of the material are greatly improved, and the tradition that a heat treatment process is taken as a final treatment process of the material is broken through.
The invention has the advantages and beneficial effects that:
the invention adopts the design of the alloy components of ultra-low carbon, low manganese and high nitrogen in the austenitic stainless steel, and controls the oxygen content of inclusions which are easy to form in the steel by purifying and smelting rare earth, controls the precipitated phase and the inclusion content in the material, ensures the roughness requirement of the material after surface treatment and the requirement of welding dust-free, finally improves the strength of the austenitic stainless steel by adopting cold deformation, refining grains, introducing a large amount of dislocation and the like, solves the technical problem that the strength and the corrosion resistance of the austenitic stainless steel cannot be considered simultaneously, and obtains the austenitic stainless steel which has lower roughness after surface treatment, better obdurability matching, excellent corrosion resistance and good welding performance under the same treatment process.
Drawings
FIG. 1 is a schematic TEM tissue of example 1.
FIG. 2 is a schematic TEM tissue of example 2.
FIG. 3 is a schematic metallographic structure of comparative example 2.
FIG. 4 is a schematic metallographic structure of comparative example 3.
Detailed Description
In the specific implementation process, a certain content of nitrogen element is added into steel, the N element is promoted to be dissolved by adopting homogenization heat treatment, finally, the strength of a material matrix is improved by adopting a cold processing (such as cold rolling and the like), the oxygen content in the steel is controlled by adopting a rare earth Se purification smelting process, the content of impurities in the material is further reduced by controlling elements such as Al, mn, si and the like, the precipitation of carbides is reduced by adopting an ultra-low carbon component control strategy, the roughness of the material after surface treatment is ensured, the secondary pollution of ultra-pure electronic special gas is avoided, and the high-strength austenitic stainless steel with excellent performance is obtained. The preparation process of the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry comprises the following steps: batching → pure smelting → casting molding → forging and hot rolling → homogenization heat treatment → cold rolling, the following method is adopted in the examples 1-5, and the specific steps are as follows:
(1) Mixing the chemical components according to the proportion, and obtaining a steel ingot through pure smelting and pouring;
(2) The ingot obtained is forged in the austenite phase region: forging temperature is 1000-1100 deg.C (1051 deg.C, 1074 deg.C, 1097 deg.C, 1001 deg.C, 1026 deg.C for examples 1-5), forging ratio is more than 6 (7.1, 6.2, 8.5, 6.3, 8.7 for examples 1-5), air cooling to room temperature after forging;
(3) Hot rolling the forged steel ingot: rolling at 1000-1100 deg.c (1054 deg.c, 1073 deg.c, 1003 deg.c, 1097 deg.c, 1025 deg.c for examples 1-5) and 10-15% (10.1%, 15.0%, 12.4%, 11.8%, 13.9% for examples 1-5) and 60-80% (61.6%, 75.0%, 74.4%, 70.8%, 69.5% for examples 1-5), hot rolling and air cooling to room temperature;
(4) Heat treatment after hot rolling: keeping the temperature of 1150-1200 ℃ (1150 ℃, 1200 ℃, 1174 ℃, 1167 ℃ and 1186 ℃ in examples 1-5) for 30-60 min (32 min, 45min, 37min, 60min and 53min in examples 1-5), and then cooling the oil to room temperature;
(5) The heat-treated plate is cold-rolled, the reduction of each pass is less than 15% (11.2%, 15.0%, 12.5%, 14.1% and 13.5% in examples 1 to 5 respectively), and the total reduction is controlled to be 40-60%. (examples 1 to 5, 44.8%, 60%, 50%, 42.3%, and 54%, respectively).
The following examples further illustrate the invention but are not intended to limit the invention thereto. After the steel in the examples and the steel in the comparative examples are subjected to purification smelting, hot working (forging and hot rolling), homogenization heat treatment and certain deformation cold working, standard tensile test samples are processed, and finally room temperature mechanical property test is carried out.
Example 1
In the embodiment, the chemical components of the high-strength austenitic stainless steel for ultra-pure electronic special gas in the semiconductor industry are as follows by weight percent: 27.12% of Cr, 32.50% of Ni, 6.12% of Mo, 1.54% of W, 0.62% of N, 33ppm of Se, 0.16% of Si, 0.02% of Mn, 48ppm of C, 30ppm of Al, 25ppm of P.
Example 2
In the embodiment, the chemical components of the high-strength austenitic stainless steel for ultra-pure electronic special gas in the semiconductor industry are as follows by weight percent: 29.27% of Cr, 38.74% of Ni, 4.21% of Mo, 0.51% of W, 0.68% of N, 39ppm of Se, 0.06% of Si, 0.01% of Mn, 36ppm of C, 40ppm of Al, 40ppm of P, 9ppm of S.
Example 3
In the embodiment, the chemical components of the high-strength austenitic stainless steel for ultra-pure electronic special gas in the semiconductor industry are as follows by weight percent: 24.12% of Cr, 26.35% of Ni, 7.96% of Mo, 2.87% of W, 0.43% of N, 21ppm of Se, 0.03% of Si, 0.03% of Mn, 41ppm of C, 35ppm of Al, 26ppm of P.
Example 4
In the embodiment, the chemical components of the high-strength austenitic stainless steel for ultra-pure electronic special gas in the semiconductor industry are as follows by weight percent: 25.62% of Cr, 29.12% of Ni, 5.12% of Mo, 0.76% of W, 0.52% of N, 26ppm of Se, 0.23% of Si, 0.04% of Mn, 36ppm of C, 24ppm of Al, 41ppm of P, 29ppm of S.
Example 5
In the embodiment, the chemical components of the high-strength austenitic stainless steel for ultra-pure electronic special gas in the semiconductor industry are as follows by weight percent: 28.73% of Cr, 36.28% of Ni, 7.07% of Mo, 2.51% of W, 0.71% of N, 35ppm of Se, 0.16% of Si, 0.02% of Mn, 27ppm of C, 31ppm of Al, 32ppm of P, 9ppm of S.
Comparative example 1
In this comparative example, the chemical composition, smelting method, hot working (forging and hot rolling), and heat treatment process of the ultra-pure austenitic stainless steel for electronic specialty gas in the semiconductor industry are exactly the same as those of example 1, but cold working is not performed, resulting in a material having a yield strength and tensile strength significantly lower than those of example 1.
Comparative example 2
In this comparative example, the austenitic stainless steel for ultra-pure electronic special gas in semiconductor industry is not added with rare earth Se, the aluminum content is as high as 0.027%, the oxygen content is 102ppm, and other chemical components, smelting methods, hot working (forging and hot rolling), heat treatment processes and cold working are the same as those in example 2.
Because a rare earth Se purification smelting process is not adopted, the oxygen content in the comparative example 2 is up to 102ppm, and in addition, because the aluminum content exceeds the range specified by the invention, the material contains large-size long-strip-shaped alumina inclusions, and the toughness of the material is reduced.
Comparative example 3
In this comparative example, the chemical components of the austenitic stainless steel for ultrapure electronic special gas in the semiconductor industry were not added with N element, and the other chemical components, the smelting method, the hot working (forging and hot rolling), the heat treatment process, and the cold rolling process were the same as those of example 2.
As shown in table 1, as compared with example 3, it can be seen that comparative example 3 contains 6.69vol.% of ferrite second phase due to the absence of N element added to comparative example 3 at a certain content, the balance structure of strong austenite forming elements and work hardening effect, resulting in significantly lower toughness than example 3.
The mechanical properties of the examples and comparative examples are shown in Table 1.
TABLE 1
As can be seen from the table 1, the nitrogen with a certain content is added and is dissolved into an austenite matrix in the process of homogenizing heat treatment, the strong austenite forming element action of N is exerted, the chromium equivalent and the nickel equivalent in the material are balanced, and the effect of ensuring that the material obtains a single stable austenite structure is achieved; the method adopts the purification smelting technology of ultra-low carbon low manganese rare earth Se, controls the contents of C and Mn in austenitic stainless steel, strictly controls the contents of elements such as Al, si, S, O and the like which are easy to form non-metallic inclusions and the like, ensures that carbides and inclusions which are easy to generate pitting corrosion are not formed on a matrix grain boundary, can ensure the surface roughness of the inner wall of a container or a conveying pipeline of the austenitic stainless steel after electrolytic polishing, effectively improves the electrolytic polishing mirror surface effect of materials, and avoids the secondary pollution of ultra-pure electron special gas; the homogenization heat treatment technology is adopted to promote the complete solid solution of nitrogen in the matrix, and the work hardening effect of nitrogen element is exerted through the final cold deformation process, so that the toughness of the material is ensured.
Fig. 1 shows the transmission structure of example 1 without work hardening, and it can be seen that the structure of the inventive material is a single austenite structure, a large number of twin crystal structures and dislocation structures exist in the matrix, the grain boundaries are clear and straight, the included angle of the grain boundaries is close to 120 °, the inventive material is a typical stable trifurcate grain boundary, no precipitated phase is observed in the grain boundaries or the interior of the grains, and the correctness of the composition and the structure design of the inventive material is proved.
Fig. 2 shows the transmission structure after cold deformation in example 2, and it can be seen that, after 60% of cold deformation, the dislocation density in the material is significantly increased, the dislocation interaction between the movable slip systems appears, an obvious cross plane slip state appears, the dislocations are greatly propagated in the slip band, a high-density dislocation wall structure is formed, and the high stress concentration is caused by the large number of dislocations at the grain boundary and the twin boundary, so that the slip lines cut through the twin crystal, the twin boundary becomes fuzzy, and the strength of the material is greatly improved.
FIG. 3 shows the metallographic structure of comparative example 2, and it can be seen that the oxygen content in the material reached 102ppm because no rare earth purification smelting technique was employed; in addition, since the content of Al is as high as 0.027%, the content of Al and Al are out of the range specified by the invention, large-size long-strip-shaped alumina inclusions are formed in the material, and the toughness of the material is deteriorated.
Fig. 4 shows the metallographic structure of comparative example 3, and it can be seen that since the strong austenite forming element N was not added, the chromium equivalent and the nickel equivalent were not balanced by the strong austenite forming element N, and thus ferrite was contained in comparative example 3 by 6.69vol.%, which deteriorated the toughness of the material.
The results of the embodiment and the comparative example prove that the idea of component design and single austenite structure control is correct, the inclusion content in steel is controlled by adopting a pure smelting process, the corrosion resistance of a matrix grain boundary is improved, and the best matching of the obdurability and the corrosion resistance of the material is obtained. The yield strength, the tensile strength and the elongation of the high-strength austenitic stainless steel for the semiconductor obtained by adopting the idea respectively reach more than 662MPa, 1037MPa and 41 percent.
Claims (8)
1. The high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry is characterized by comprising the following chemical components in percentage by weight: 24.0 to 30.0 percent of Cr, 25.0 to 40.0 percent of Ni, 4.0 to 8.0 percent of Mo, 0 to 3.0 percent of W, 0.1 to 1.0 percent of N, 0 to 0.01 percent of Se, 0.3 percent of Si, 0.01 percent of C, 0.05 percent of Mn, 0.01 percent of Al, 0.005 percent of P, 0.001 percent of S, 0.004 percent of O and the balance of iron.
2. The high strength austenitic stainless steel for ultra pure electronic specialty gas in semiconductor industry as claimed in claim 1, wherein, preferably, N:0.4 to 0.8 percent.
3. The high-strength austenitic stainless steel for ultra-pure electronic special gas in semiconductor industry as claimed in claim 1, wherein, preferably, se is 0.002-0.004%.
4. A method for preparing the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry according to any one of claims 1 to 3, characterized by comprising the following steps:
(1) Mixing the chemical components in proportion, and obtaining steel ingots through purification smelting and casting;
(2) Forging the obtained steel ingot in an austenite phase region;
(3) Hot rolling the forged steel ingot: the rolling temperature is 1000-1100 ℃, the rolling reduction of each pass is controlled to be 10-15%, the total rolling reduction is controlled to be 60-80%, and the steel is air-cooled to room temperature after hot rolling;
(4) Carrying out heat treatment after hot rolling;
(5) And cold rolling the heat-treated plate.
5. The method for preparing the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry according to claim 4, wherein in the step (2), the forging process comprises the following steps: the forging temperature is 1000-1100 ℃, the forging ratio is more than 6.0, and the forging is carried out by air cooling to the room temperature.
6. The preparation method of the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry according to the claim 4, characterized in that in the step (4), the heat treatment process is as follows: keeping the temperature of 1150-1200 ℃ for 30-60 min, and then carrying out oil cooling to the room temperature.
7. The method for preparing the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry according to the claim 4, wherein in the step (5), the cold rolling process comprises the following steps: the reduction of each pass is less than 15 percent, and the total reduction is controlled to be 40 to 60 percent.
8. The method for preparing the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry according to claim 7, wherein the yield strength of the high-strength austenitic stainless steel for the ultra-pure electronic special gas in the semiconductor industry after cold rolling is more than 650MPa, the tensile strength is more than 1000MPa, and the elongation is more than 40%.
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