CN116005082A - High-purity austenitic stainless steel for electronic special gas in semiconductor industry and preparation method thereof - Google Patents
High-purity austenitic stainless steel for electronic special gas in semiconductor industry and preparation method thereof Download PDFInfo
- Publication number
- CN116005082A CN116005082A CN202211622329.2A CN202211622329A CN116005082A CN 116005082 A CN116005082 A CN 116005082A CN 202211622329 A CN202211622329 A CN 202211622329A CN 116005082 A CN116005082 A CN 116005082A
- Authority
- CN
- China
- Prior art keywords
- percent
- stainless steel
- austenitic stainless
- purity
- semiconductor industry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000963 austenitic stainless steel Inorganic materials 0.000 title claims abstract description 54
- 239000004065 semiconductor Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 238000003723 Smelting Methods 0.000 claims abstract description 18
- 229910052796 boron Inorganic materials 0.000 claims abstract description 18
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 18
- 238000005242 forging Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005098 hot rolling Methods 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 58
- 239000010959 steel Substances 0.000 claims description 58
- 239000007789 gas Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 25
- 238000003466 welding Methods 0.000 claims description 23
- 238000000746 purification Methods 0.000 claims description 15
- 238000005096 rolling process Methods 0.000 claims description 14
- 239000000428 dust Substances 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 12
- 238000005097 cold rolling Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims 1
- 150000002835 noble gases Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 32
- 239000011651 chromium Substances 0.000 abstract description 24
- 239000011572 manganese Substances 0.000 abstract description 22
- 238000013461 design Methods 0.000 abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005482 strain hardening Methods 0.000 abstract description 10
- 238000005266 casting Methods 0.000 abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000005260 corrosion Methods 0.000 description 21
- 230000007797 corrosion Effects 0.000 description 21
- 230000000694 effects Effects 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 229910052761 rare earth metal Inorganic materials 0.000 description 15
- 238000005498 polishing Methods 0.000 description 14
- 150000002910 rare earth metals Chemical class 0.000 description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000006104 solid solution Substances 0.000 description 8
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000000265 homogenisation Methods 0.000 description 6
- 229910000914 Mn alloy Inorganic materials 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000004807 localization Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Abstract
The invention relates to high-purity austenitic stainless steel for electronic special gas in the semiconductor industry and a preparation method thereof, and belongs to the technical field of materials. The austenitic stainless steel comprises the following chemical components in percentage by weight: 16.0 to 18.0 percent of Cr, 12.0 to 15.0 percent of Ni, 2.0 to 3.0 percent of Mo, 0.1 to 1.0 percent of N, 0.001 to 0.02 percent of B, 0.0001 to 0.01 percent of Ce, 0.1 percent of Si, 0.01 percent of C, 0.05 percent of Mn, 0.01 percent of Al, 0.004 percent of P, 0.002 percent of S, 0.003 percent of O and the balance of iron. The preparation method of the austenitic stainless steel comprises the following steps: batching, purifying smelting, casting molding, forging and hot rolling, heat treatment and cold working. The invention adopts the design idea of the component with ultra-low carbon and low manganese, controls the equivalent of chromium and the equivalent of nickel, and ensures that a complete austenite structure is obtained.
Description
Technical Field
The invention relates to high-purity austenitic stainless steel for electronic special gas in the semiconductor industry and a preparation method thereof, and belongs to the technical field of materials.
Background
The semiconductor industry uses high purity electron specialty gases (electron specialty gases) as the basis for the modern integrated circuit industry as a carrier for substances produced by Integrated Circuits (ICs). The high-purity electronic special gas (the volume purity reaches 6 pieces of 9, namely 99.9999%) is a key factor for promoting the progress of the semiconductor industry, and the high-purity electronic special gas is used as the upstream of an industrial chain of semiconductors and the like and is one of the weakest links in a high-end electrochemical process chain.
High-purity electron gas, which is known as blood in high-end electrochemical process chain, is a core product for measuring process technology, and three technical barriers exist at present: 1) The difficulty of the deep purification technology is high, 2) packaging and storage cannot be kept over, and the production and application of the ultra-high purity gas all require the use of a high-quality gas packaging and storage container; 3) The component analysis and inspection concept of the electronic special gas is behind, and the research and development of the analysis and detection technology in the field of the production and application of the electronic special gas are not paid attention to. Localization of special electronic gas is imperative.
At present, most of domestic gas companies still have single supply products, the material used by the semiconductor pressure vessel is basically 316L austenitic stainless steel, the development requirements of the semiconductor industry in China can not be met, and the aspects of a storage and transportation vessel, a corresponding gas delivery pipeline, a valve and an interface of high-purity special gas used in the high-end field of integrated circuits and the like have not been broken through, and the material and surface treatment process of the pressure vessel used by the special gas in China are behind the whole technology of the prior art, so that the corresponding material and process standard system between the material selection of the high-purity electronic special gas and a gas cylinder, the inner wall surface treatment and the like have not been established. Therefore, in order to promote the development of the high-purity electron special gas and promote the localization of the high-purity electron special gas, the development of the high-purity austenitic stainless steel required by the gas cylinder materials required by special gas storage and transportation is required.
Disclosure of Invention
The invention aims to provide high-purity austenitic stainless steel for special electron gas in the semiconductor industry and a preparation method thereof, and adopts the innovative design idea of ultralow-carbon low-manganese alloy components, improves the surface finish of electrolytic polishing by reducing the number of corrosion-prone carbides on a grain boundary, increases certain nitrogen content, controls chromium equivalent and nickel equivalent, ensures that a complete martensitic structure is obtained, and fully plays the strengthening effect of solid solution nitrogen through cold working, thereby improving the strength and hardness of an austenitic matrix.
The technical scheme of the invention is as follows:
the austenitic stainless steel for the high-purity electron special gas in the semiconductor industry comprises the following chemical components in percentage by weight: 16.0 to 18.0 percent of Cr, 12.0 to 15.0 percent of Ni, 2.0 to 3.0 percent of Mo, 0.1 to 1.0 percent of N, 0.001 to 0.02 percent of B, 0.0001 to 0.01 percent of Ce, 0.1 percent of Si, 0.01 percent of C, 0.05 percent of Mn, 0.01 percent of Al, 0.004 percent of P, 0.002 percent of S, 0.003 percent of O and the balance of iron.
The austenitic stainless steel for the high-purity electron special gas in the semiconductor industry preferably comprises the following components: 0.2 to 0.5 percent.
The austenitic stainless steel for the high-purity electron gas in the semiconductor industry is preferably 0.004-0.008% of B and 0.001-0.005% of Ce.
The preparation method of the austenitic stainless steel for the high-purity electron gas in the semiconductor industry comprises the following steps:
(1) Mixing the chemical components in proportion, and obtaining a steel ingot 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 1100-1200 ℃, the rolling reduction of each pass is controlled to be 20-30%, the total rolling reduction is controlled to be 60-80%, and the air cooling is carried out to room temperature after hot rolling;
(4) Carrying out heat treatment after hot rolling;
(5) And cold rolling the heat-treated plate.
The preparation method of the austenitic stainless steel for the high-purity electron gas in the semiconductor industry comprises the following steps of: forging temperature is 1100-1200 deg.c, forging ratio is over 6, and air cooling to room temperature.
The preparation method of the austenitic stainless steel for the high-purity electron gas in the semiconductor industry comprises the following steps of: and (3) carrying out water quenching to room temperature after preserving heat for 20-40 min at 1150+/-50 ℃.
The preparation method of the austenitic stainless steel for the high-purity electron gas in the semiconductor industry comprises the following steps of: the rolling reduction of each pass is less than 20%, and the total rolling reduction is controlled to be 30% -50%.
The preparation method of the austenitic stainless steel for the high-purity electronic special gas in the semiconductor industry is characterized in that the yield strength of the austenitic stainless steel for the high-purity electronic special gas in the semiconductor industry after cold rolling is more than 350MPa, the tensile strength is more than 800MPa, the elongation is more than 40%, and the requirement of no dust in welding is met.
The main element content ranges in the invention are described as follows:
cr: chromium is an important element in high-chromium stainless steel, and is a primary element determining corrosion resistance of stainless steel because chromium improves corrosion resistance of steel itself while allowing the steel to easily form a chromium oxide layer thereon, but when the Cr content is less than 15%, the minimum corrosion resistance required for stainless steel cannot be obtained. On the other hand, when the Cr content exceeds 18%, intermetallic compounds are likely to precipitate, resulting in deterioration of hot workability and mechanical properties. Therefore, the chromium content in the invention is controlled as follows: 16.0 to 18.0wt%.
Ni: nickel is an important element for controlling the complete austenite structure of austenitic stainless steel. In order to ensure the stable austenite structure, when the Ni content is less than 10%, the austenite structure is unstable, and on the other hand, when the Ni content is high, the influence of Ni tends to saturate after exceeding a certain content, and at the same time, the production cost gradually increases. Therefore, in order to obtain a complete austenite structure and economy, the range of Ni content is limited to 12.0 to 15.0wt%.
Mo: the corrosion resistance of austenitic stainless steel can be obviously improved by adding a certain content of molybdenum, but molybdenum is ferrite forming element, the capacity is equivalent to that of chromium, and the excessive Mo content can promote the formation of high-temperature ferrite phase, and the processability and welding performance of the material are 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: 2.0 to 3.0 weight percent.
N and B: nitrogen is a strong austenite forming element, enlarges the austenite phase region, reduces the ferrite phase region, and can inhibit the formation of high-temperature ferrite in steel. Because the austenitic stainless steel adopts the component design thought of ultralow carbon and low manganese, in order to obtain a full austenitic structure under the condition of certain nickel content, nitrogen with certain content is added into the steel, and the nickel equivalent and the chromium equivalent are balanced, so that the full austenitic structure is ensured to be obtained. In addition, nitrogen can greatly improve the strength of the steel in the final cold working process, but the nitrogen content is too high to easily form CrN, so that the corrosion resistance of the steel is reduced. The grain is refined by adding a part of boron into the steel, in addition, the boron is an element capable of generating nitride, and B and N are added into austenitic stainless steel in a compounding way to form extremely fine BN, so that the processing performance can be obviously improved. To achieve this effect, the N content should be between 0.01 and 1.0% and the B content should be above 0.001%. On the other hand, when the B content exceeds 0.01%, the nitride precipitates excessively, resulting in a decrease in corrosion performance and work hardening ability. The optimized nitrogen and boron contents in the steel according to the invention are therefore respectively: 0.2 to 0.5 weight percent of N and 0.004 to 0.008 weight percent of B.
Ce: the steel contains a certain amount of rare earth, so that the plasticity and toughness of the steel can be obviously improved, and the transverse performance and low-temperature toughness of the steel are improved. The rare earth has the functions of purifying molten steel, modifying, mixing and microalloying, and is beneficial to improving the cold stamping formability and corrosion resistance of the steel. In addition, since selenium has an effect of improving arc stability in arc welding and has an effect of suppressing a change in shape of 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 impairing corrosion resistance and seriously deteriorating the performance of the material. Therefore, the content of rare earth Ce in the steel is optimally controlled as follows: 0.001 to 0.005 weight percent of Ce.
Si: silicon, while deoxidizing to clean the steel, also forms oxide inclusions, thereby affecting the subsequent electropolishing effect and weld dust generation. When the Si content exceeds 0.50%, inclusions become large, and dust-free characteristics under welding conditions are particularly affected. Therefore, it is necessary to reduce the Si content, and the content of Si in the steel of the present invention is optimally controlled as follows: si <0.1wt%.
C: carbon and chromium precipitate M at grain boundaries and welds 23 C 6 The type carbide reduces the corrosion resistance of the material, influences the electrolytic polishing effect of the material, and considers that the steel provided by the invention is used for a strong corrosive gas. Therefore, by adopting the component design thought of ultra-low carbon, the content of C in the steel is optimally controlled as follows: c (C)<0.01wt％。
Mn: manganese, although it has the same deoxidizing effect as silicon to purify steel, is a most detrimental element of the dust-free nature of the material because of its volatile nature, and a large amount of dust is easily generated during the welding process. Especially when the Mn content exceeds 0.2%, the amount of dust generated during welding increases drastically. In addition, mn and S are easy to form MnS inclusion, the mirror effect after electrolytic polishing is affected, and the content of Mn element is strictly controlled according to the welding dust-free characteristic of the material and the polishing mirror requirement. Therefore, the content of Mn in the steel is optimally controlled as follows: mn <0.05wt%.
Al: aluminum has the effect of deoxidizing the steel to purify the steel. However, 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 process of the material, alumina inclusions are generated in the case that the oxygen content of the surface of the material is extremely low, which is one of the causes of welding dust generation. Therefore, for austenitic stainless steel, it is necessary to reduce the aluminum content. Therefore, the content of Al in the steel is optimally controlled as follows: al <0.01wt%.
S, P: the main inclusion forming elements and the harmful elements in the steel are respectively. Sulfur and manganese tend to form manganese sulfide inclusions that affect the mirror effect after electropolishing, and in addition, the inclusions have a very detrimental effect on the impact toughness and creep properties of the steel while compromising the creep properties of the steel. Phosphorus increases the ductile-brittle transition temperature of steel sharply, increasing the cold brittleness of steel. Therefore, the content control of sulfur and phosphorus in the steel of the invention is very strict: s <0.002wt% and P <0.004wt%.
O: oxygen is a major element in steel that produces oxide inclusions, and therefore, in order to reduce inclusions in steel and to ensure purification of steel, the oxygen content therein must be reduced as much as possible. Furthermore, oxide inclusions tend to accumulate and grow at the weld during the welding process. In order to reduce the amount of dust particles during welding, the range of O content in the steel is limited to an extremely low level so as not to adversely affect the dust-free properties of the material. Therefore, the control of the oxygen content in the steel of the invention is extremely strict: o <0.003wt%.
The innovative design concept of the invention has four points, as follows:
1) Creative design of the components of the ultralow-carbon low-manganese alloy: carbon and chromium easily form carbide in the heat treatment process, on one hand, cr in solid solution in the material is reduced, so that the corrosion performance of the material is reduced, on the other hand, the carbide easily peels off after the electrolytic polishing of the material, and the roughness of the material after the electrolytic polishing is affected, so that secondary pollution of high-purity electron special gas is caused. Manganese has two effects, the first being relatively low in vapor pressure and prone to high dust contamination during welding and the second being prone to MnS inclusion formation, thereby affecting electropolishing roughness. The design idea of ultralow-carbon low-manganese alloy is adopted, S in steel is controlled below 10ppm, chromium carbide and MnS inclusion are avoided, the surface roughness requirement of the material after electrolytic polishing is ensured, and the welding performance of the material is obviously improved.
2) Composite addition of nitrogen and boron: because the design of the alloy components of ultralow carbon and low manganese is adopted, the nickel equivalent of the material is influenced by the content of strong austenite forming elements such as carbon, manganese and the like, and the whole austenite structure cannot be obtained, and therefore, the nitrogen content is controlled within the range of 0.2-0.5% by adding and optimizing the content of strong austenite forming elements equivalent to carbon, and on one hand, the chromium equivalent and the nickel equivalent in steel are balanced by the strong austenite stabilizing effect of most of N elements dissolved in a matrix through heat treatment, so that the occurrence of ferrite which is caused by the ultralow carbon and low manganese and deteriorates the comprehensive performance of the material is avoided; secondly, solid solution nitrogen in the austenite can reduce close-packed incomplete dislocation in the steel, limit dislocation movement containing interstitial atomic groups, and improve the strength of austenitic stainless steel on the basis of not damaging the plasticity and toughness of the steel; in addition, by adding boron in a certain content, BN in a hard certain content is formed in the steel, thereby remarkably improving the machinability of austenitic stainless steel.
3) Rare earth purification smelting technology: by adopting the rare earth purification smelting technology, the content of harmful elements such as Al, P, S, O and the like which are easy to form inclusion in the steel is strictly controlled, the content of Al is controlled below 0.01%, the content of O is controlled below 30ppm, and the content of S is controlled below 20ppm, so that the inclusion is further reduced, the roughness of the surface of the material after electrolytic polishing is affected, and the secondary pollution of high-purity electron special gas is avoided.
4) Final cold deformation process control: the traditional method that the heat treatment structure of the material is regulated and controlled to be final treatment is broken, the grains are further refined by controlling the cold deformation within 30% -50%, a large number of dislocation is introduced into the matrix, and the toughness and corrosion resistance of the material are further improved by utilizing the work hardening of nitrogen.
The invention has the advantages and beneficial effects that:
1. according to the invention, through the chemical composition design of ultralow carbon and low manganese in austenitic stainless steel and the addition of rare earth purification smelting, the content of inclusion elements which are easy to generate such as Al, mn, si and O is reduced, the content of precipitated phases and inclusions in the material is strictly controlled, the corrosion resistance of the material is improved, the high purity of austenitic stainless steel is realized, the surface smoothness and roughness of the material after electrolytic polishing are ensured, the secondary pollution of high-purity electron special gas is avoided, the dust content in the welding process is reduced by the high purity and low manganese design of the material, and the requirement of low dust in the welding process is met. In addition, under the design concept of the ultralow-carbon low-manganese alloy, in order to obtain a single austenite structure, the N element content in the alloy is optimized by compositely adding N and B elements, the nickel equivalent and the chromium equivalent of the alloy are balanced, and the machining performance of the material is improved. Finally, the strength and corrosion resistance of the austenitic stainless steel are improved by adopting cold deformation, refining grains, introducing a large amount of dislocation and the like, so that the austenitic stainless steel with high purity, high strength and toughness collocation and excellent welding performance is obtained.
2. The invention adopts an innovative design idea of 'ultra-low carbon and low manganese', controls chromium equivalent and nickel equivalent, ensures to obtain a complete austenite structure, adopts a rare earth purification smelting process to control the content of inclusions in steel, ensures the mirror effect after electrolytic polishing of materials, prevents secondary pollution of semiconductor high-purity electron special gas, meets the requirement of no dust in material welding by reducing the content of elements such as Al, mn, si, O and the like, and ensures the toughness requirement and the cutting processability of the materials by compounding and adding N and B with certain content into steel.
3. According to the invention, through the composite addition of nitrogen and boron in a proper proportion, most of N in solid solution in the material is ensured, the high-temperature ferrite which is caused by the design of ultralow carbon and low manganese components and deteriorates the material performance is avoided, the strength of the material can be greatly improved through cold working, and the cutting performance of austenitic stainless steel can be obviously improved through forming BN with a certain content by N and B.
4. The invention adopts rare earth purification smelting technology, improves the purity by greatly reducing the oxygen content in steel, and in addition, the rare earth Ce can improve the stability of electric arc in the welding process, ensures the welding performance, obtains austenitic stainless steel with high purity, high strength and toughness and excellent welding performance, and meets the requirement of no dust in material welding.
Drawings
FIG. 1 is a schematic diagram of the metallographic structure of example 1.
Fig. 2 is a schematic TEM structure of example 2.
FIG. 3 is a schematic diagram of the metallographic structure of comparative example 2.
FIG. 4 is a schematic diagram of the metallographic structure of comparative example 3.
Detailed Description
In the specific implementation process, nitrogen and boron with certain content are added into steel in a compounding way, a lower homogenization heat treatment is adopted to promote solid solution of N element, a BN precipitation phase with certain content is reserved, the cutting processing performance of the material is provided, finally, the strength of a material matrix is improved in a cold processing mode, the oxygen content in the steel is controlled by adopting a rare earth purification smelting process, the inclusion content in the material is further reduced by controlling elements such as Al, mn and Si, an ultralow carbon component control strategy is adopted, carbide precipitation is reduced, the mirror effect of the surface of the material after electrolytic polishing is further improved, secondary pollution of high-purity electron special gas is prevented, and the optimal collocation of the material strength and corrosion resistance is obtained.
The preparation process of the austenitic stainless steel for the high-purity electron special gas in the semiconductor industry comprises the following steps: batching, purifying smelting, casting molding, forging and hot rolling, homogenizing heat treatment and cold rolling, wherein the following methods are adopted in 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 purification smelting and casting;
(2) Forging the obtained steel ingot in an austenite phase region: forging temperature is 1100-1200 ℃ (examples 1-5 are 1150 ℃, 1175 ℃, 1198 ℃, 1107 ℃, 1124 ℃), forging ratio is more than 6 (examples 1-5 are 7.4, 6.1, 8.2, 6.4, 8.3 respectively), and air cooling to room temperature is carried out after forging;
(3) Hot rolling the forged steel ingot: the rolling temperature is 1100-1200 ℃ (1152 ℃ and 1176 ℃ in examples 1-5 are respectively 1103 ℃, 1196 ℃ and 1125 ℃), the rolling reduction of each pass is controlled to be 20-30% (25.5%, 26.6%, 23.5%, 22.4% and 25.8% in examples 1-5), the total rolling reduction is controlled to be 60-80% (76.5%, 79.8%, 70.5%, 67.2% and 77.4% in examples 1-5), and the hot rolling is carried out and then air cooling is carried out to room temperature;
(4) And (3) performing heat treatment after hot rolling: heat preservation is carried out for 20min to 40min (21 min, 30min, 25min, 39min and 27min in examples 1 to 5 respectively) at 1150+/-50 ℃ (1105 ℃, 1200 ℃, 1151 ℃, 1172 ℃ and 1124 ℃ in examples 1 to 5 respectively), and then water quenching is carried out to room temperature;
(5) The heat-treated sheet was cold-rolled to a reduction of less than 20% per pass (examples 1 to 5 were 15.2%, 17.6%, 17.7%, 19.5% and 16.5%, respectively), and the total reduction was controlled to 30% to 50%. (examples 1 to 5 were 30.4%, 35.2%, 35.4%, 39%, 49.5%) respectively.
The following examples further illustrate the invention, but are not intended to limit it. The steels in examples and comparative examples were subjected to test of room temperature tensile property test specimens after purification smelting, hot working (forging and hot rolling), homogenization heat treatment and cold rolling with a certain deformation amount.
Example 1
In the embodiment, the austenitic stainless steel for high-purity electron gas in the semiconductor industry comprises the following chemical components in percentage by weight: 16.85% of Cr, 13.52% of Ni, 2.52% of Mo, 0.36% of N, 0.06% of Si, 0.04% of Mn, 55ppm of B, 31ppm of Ce, 50ppm of C, 60ppm of Al, 35ppm of P, 8ppm of S, 20ppm of O and the balance of iron.
Example 2
In the embodiment, the austenitic stainless steel for high-purity electron gas in the semiconductor industry comprises the following chemical components in percentage by weight: 17.85% of Cr, 12.15% of Ni, 2.13% of Mo, 0.49% of N, 0.05% of Si, 0.02% of Mn, 76ppm of B, 45ppm of Ce, 55ppm of C, 45ppm of Al, 25ppm of P, 10ppm of S, 15ppm of O and the balance of iron.
Example 3
In the embodiment, the austenitic stainless steel for high-purity electron gas in the semiconductor industry comprises the following chemical components in percentage by weight: 16.14% of Cr, 14.78% of Ni, 2.96% of Mo, 0.21% of N, 0.08% of Si, 0.03% of Mn, 41ppm of B, 14ppm of Ce, 80ppm of C, 70ppm of Al, 38ppm of P, 15ppm of S, 22ppm of O and the balance of iron.
Example 4
In the embodiment, the austenitic stainless steel for high-purity electron gas in the semiconductor industry comprises the following chemical components in percentage by weight: 17.48% of Cr, 12.75% of Ni, 2.23% of Mo, 0.42% of N, 0.05% of Si, 0.04% of Mn, 69ppm of B, 41ppm of Ce, 75ppm of C, 65ppm of Al, 25ppm of P, 10ppm of S, 12ppm of O and the balance of iron.
Example 5
In the embodiment, the austenitic stainless steel for high-purity electron gas in the semiconductor industry comprises the following chemical components in percentage by weight: 16.51% Cr, 14.30% Ni, 2.76% Mo, 0.28% N, 0.06% Si, 0.03% Mn, 51% B, 23% Ce, 65% C, 50% Al, 35% P, 17% S, 26% O and the balance Fe.
Comparative example 1
In this comparative example, the chemical composition, smelting method, hot working (forging and hot rolling), and heat treatment of austenitic stainless steel for high purity electron gas in the semiconductor industry were exactly the same as in example 1, but cold working was not performed, resulting in a material having significantly lower yield strength and tensile strength than in example 1.
Comparative example 2
In this comparative example, the chemical components of austenitic stainless steel for high purity electronics and special gas in the semiconductor industry were not added with N element, and other chemical components, the smelting method, hot working (forging and hot rolling), homogenization heat treatment and cold rolling process were the same as in example 2.
As shown in table 1, it can be seen from comparison with example 2 that since a certain amount of N element is not added in comparative example 2, there is no work hardening of strong austenite forming element N, comparative example 2 contains 5.75% of ferrite second phase, resulting in a material having significantly lower i toughness and corrosion performance than example 2.
Comparative example 3
In this comparative example, the austenitic stainless steel for high purity electron gas in the semiconductor industry was free of rare earth Ce, had an aluminum content of up to 0.016%, and an oxygen content of up to 64ppm, and other chemical components, smelting methods, hot working (forging and hot rolling), heat treatment and cold working were the same as those in example 3.
The oxygen content in comparative example 3 is up to 64ppm because the rare earth purification smelting process is not adopted, and the aluminum content exceeds the specified range of the invention, so that the material contains long alumina inclusion, and the toughness of the material is reduced.
The mechanical properties of examples and comparative examples are shown in Table 1.
TABLE 1
| Sequence number | Yield strength/MPa | Tensile strength/MPa | Elongation/% |
| Example 1 | 486 | 914 | 51 |
| Example 2 | 564 | 965 | 45 |
| Example 3 | 421 | 864 | 54 |
| Example 4 | 514 | 942 | 48 |
| Example 5 | 375 | 825 | 57 |
| Comparative example 1 | 280 | 550 | 65 |
| Comparative example 2 | 265 | 534 | 35 |
| Comparative example 3 | 342 | 784 | 29 |
As can be seen from table 1, according to the present invention, by adding a certain amount of nitrogen, the nitrogen is dissolved in the austenite matrix during the homogenization heat treatment process, the strong austenite forming element action of N is exerted, the chromium equivalent and the nickel equivalent are balanced, and the effect of obtaining a single stable austenite structure is achieved; adopts the purification smelting technology of ultralow-carbon low-manganese rare earth, controls the content of C in austenitic stainless steel to be less than 100ppm, strictly controls the content of elements such as Al, si, S, O and the like which are easy to form nonmetallic inclusions and the like, and adopts the homogenization heat treatment technology to further reduce Cr 23 C 6 The precipitation of carbide ensures that carbide and inclusion which are easy to cause pitting are not formed on the grain boundary of the matrix, can ensure the roughness of the material after electrolytic polishing, effectively improves the electrolytic polishing mirror surface effect of the material and improves the corrosion resistance of the austenitic stainless steelThe method comprises the steps of carrying out a first treatment on the surface of the The final cold deformation process further plays a solid solution strengthening effect of N, refines grains and further plays a double effect of improving strength and corrosion resistance.
As shown in fig. 1, the microstructure of the steel after the aqua regia corrosion in example 1 of the present invention is a single austenite structure, and when the cold deformation amount is 40%, the grain refinement is remarkable, and the strip structure is remarkable along the rolling direction.
As shown in FIG. 2, the transmission structure of cold deformation in the embodiment 2 of the invention shows that the austenite steel has no harmful phases such as carbide, inclusion and the like on the grain boundary, the purity of the material is higher, the correctness of the design idea of the material composition is proved, meanwhile, the dislocation density is obviously increased due to the 50% cold deformation of the material, dislocation interaction between movable sliding systems occurs in an obvious cross plane sliding state, dislocation is greatly proliferated in a sliding band, high-density dislocation is formed in the sliding band, and the dislocation on the crossed sliding surface is mutually intersected to form a cutting order, so that the work hardening of the material is further improved.
As shown in FIG. 3, it is apparent from the metallographic structure of comparative example 2 of the present invention that the addition of the strong austenite forming element N results in 5.75% ferrite in comparative example 2, deteriorating the toughness of the material, and that micro-cells can be locally formed due to the presence of the second phase, greatly decreasing the corrosion resistance of the material.
As shown in FIG. 4, it is apparent from the metallographic structure of comparative example 3 of the present invention that the oxygen content in the material was 64ppm, which was not within the range defined in the present invention, and that the Al content was 160ppm, which was not within the range defined in the present invention, resulted in the formation of long alumina inclusions, which deteriorated the toughness of the material.
The results of the examples and the comparative examples show that by adopting the design concept of ultra-low carbon and low manganese components and adopting the rare earth purification smelting process, the invention combines and adds a certain content of N and B elements into austenitic stainless steel, strictly controls the content of Al, si, S and the like which are easy to form inclusion elements in the material, ensures the mirror effect of the surface of the material after electrolytic polishing, realizes complete solid solution of N in an austenitic matrix on the premise of ensuring uniform distribution of a certain content of BN by a homogenization heat treatment technology, further plays the solid solution strengthening effect of nitrogen in the final cold rolling process, further improves the toughness of austenitic stainless steel, breaks through the technical problem of combining the toughness and the corrosion resistance of austenitic stainless steel, and meets the requirement of no dust in welding. The yield strength, tensile strength and elongation of the austenitic stainless steel after cold rolling respectively reach more than 375MPa, 825MPa and 45 percent.
Claims (8)
1. The austenitic stainless steel for the high-purity electron gas in the semiconductor industry is characterized by comprising the following chemical components in percentage by weight: 16.0 to 18.0 percent of Cr, 12.0 to 15.0 percent of Ni, 2.0 to 3.0 percent of Mo, 0.1 to 1.0 percent of N, 0.001 to 0.02 percent of B, 0.0001 to 0.01 percent of Ce, 0.1 percent of Si, 0.01 percent of C, 0.05 percent of Mn, 0.01 percent of Al, 0.004 percent of P, 0.002 percent of S, 0.003 percent of O and the balance of iron.
2. The austenitic stainless steel for high purity electronics and gas of claim 1, wherein the preferred N:0.2 to 0.5 percent.
3. The austenitic stainless steel for high-purity electronic off-gas in semiconductor industry according to claim 1, wherein B is preferably 0.004-0.008% and Ce is preferably 0.001-0.005%.
4. A method for preparing the austenitic stainless steel for high-purity electron noble gases in the semiconductor industry, which is characterized by comprising the following steps:
(1) Mixing the chemical components in proportion, and obtaining a steel ingot 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 1100-1200 ℃, the rolling reduction of each pass is controlled to be 20-30%, the total rolling reduction is controlled to be 60-80%, and the air cooling is carried out 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 high-purity austenitic stainless steel for electronic gases in the semiconductor industry according to claim 4, wherein in step (2), the forging process is as follows: forging temperature is 1100-1200 deg.c, forging ratio is over 6, and air cooling to room temperature.
6. The method for preparing high-purity austenitic stainless steel for electronic gases in the semiconductor industry according to claim 4, wherein in step (4), the heat treatment process is as follows: and (3) carrying out water quenching to room temperature after preserving heat for 20-40 min at 1150+/-50 ℃.
7. The method for preparing high-purity austenitic stainless steel for electronic gas in the semiconductor industry according to claim 4, wherein in step (5), the cold rolling process is as follows: the rolling reduction of each pass is less than 20%, and the total rolling reduction is controlled to be 30% -50%.
8. The method for preparing the austenitic stainless steel for the high-purity electronic special gas in the semiconductor industry, which is disclosed in claim 7, is characterized in that the austenitic stainless steel for the high-purity electronic special gas in the semiconductor industry after cold rolling has the yield strength of more than 350MPa, the tensile strength of more than 800MPa and the elongation of more than 40 percent, and meets the requirement of no dust in welding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211622329.2A CN116005082A (en) | 2022-12-16 | 2022-12-16 | High-purity austenitic stainless steel for electronic special gas in semiconductor industry and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211622329.2A CN116005082A (en) | 2022-12-16 | 2022-12-16 | High-purity austenitic stainless steel for electronic special gas in semiconductor industry and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116005082A true CN116005082A (en) | 2023-04-25 |
Family
ID=86025876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211622329.2A Pending CN116005082A (en) | 2022-12-16 | 2022-12-16 | High-purity austenitic stainless steel for electronic special gas in semiconductor industry and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116005082A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116623105A (en) * | 2023-07-24 | 2023-08-22 | 中科艾尔(北京)科技有限公司 | Ultra-high purity 316L stainless steel and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5340534A (en) * | 1992-08-24 | 1994-08-23 | Crs Holdings, Inc. | Corrosion resistant austenitic stainless steel with improved galling resistance |
| US5830408A (en) * | 1993-10-20 | 1998-11-03 | Sumitomo Metal Industries, Ltd. | Stainless steel for high-purity gases |
| CN112522619A (en) * | 2020-11-26 | 2021-03-19 | 中国科学院金属研究所 | Concentrated nitric acid corrosion resistant high-strength austenitic stainless steel and preparation method thereof |
| CN113122782A (en) * | 2021-04-21 | 2021-07-16 | 浙江中煤机械科技有限公司 | Stainless steel for pump head body and preparation method thereof |
-
2022
- 2022-12-16 CN CN202211622329.2A patent/CN116005082A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5340534A (en) * | 1992-08-24 | 1994-08-23 | Crs Holdings, Inc. | Corrosion resistant austenitic stainless steel with improved galling resistance |
| US5830408A (en) * | 1993-10-20 | 1998-11-03 | Sumitomo Metal Industries, Ltd. | Stainless steel for high-purity gases |
| CN112522619A (en) * | 2020-11-26 | 2021-03-19 | 中国科学院金属研究所 | Concentrated nitric acid corrosion resistant high-strength austenitic stainless steel and preparation method thereof |
| CN113122782A (en) * | 2021-04-21 | 2021-07-16 | 浙江中煤机械科技有限公司 | Stainless steel for pump head body and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 金心等: "《稀土金属在钢铁中的应用 译文集》", 30 June 1965, 中国工业出版社, pages: 194 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116623105A (en) * | 2023-07-24 | 2023-08-22 | 中科艾尔(北京)科技有限公司 | Ultra-high purity 316L stainless steel and preparation method thereof |
| CN116623105B (en) * | 2023-07-24 | 2023-10-31 | 中科艾尔(北京)科技有限公司 | Ultra-high purity 316L stainless steel and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111363973A (en) | Super-thick container steel plate with excellent core low-temperature impact toughness and manufacturing method thereof | |
| CN109988971B (en) | Method for producing ultra-grade pure high-speed tool steel | |
| CN110699599B (en) | Q345R steel for ultralow temperature and manufacturing method thereof | |
| CN112522635B (en) | High-carbon high-chromium martensitic stainless steel for cutter and preparation method thereof | |
| CN112941406B (en) | Stainless steel for knife and scissors | |
| CN116005082A (en) | High-purity austenitic stainless steel for electronic special gas in semiconductor industry and preparation method thereof | |
| CN110592480A (en) | Thick Q345R steel plate with excellent low-temperature impact toughness at core and manufacturing method thereof | |
| CN108220813B (en) | Super-grade duplex stainless steel and alloy component optimization design method thereof | |
| CN114107826A (en) | Nickel-based high-temperature alloy and preparation method thereof | |
| CN109423569B (en) | Steel for low-temperature pressure vessel and manufacturing method thereof | |
| CN113737090A (en) | High-strength and high-toughness alloy structural steel and preparation method thereof | |
| CN110172638B (en) | High-temperature carburized gear steel and production method thereof | |
| CN114574762B (en) | Steel for high-strength-toughness corrosion-resistant underwater Christmas tree valve body smelted under high scrap steel ratio, heat treatment method and production method thereof | |
| CN109047693A (en) | A kind of economical HIC resistance pipeline steel plate X52MS and its manufacturing method of TMCP delivery | |
| CN113337783A (en) | Production method of barium-cleaned iron-chromium-aluminum alloy | |
| CN113234997A (en) | Novel manganese nitrogen chromium heat-resistant steel and manufacturing method thereof | |
| CN115874103A (en) | High-strength austenitic stainless steel for ultra-pure electronic special gas in semiconductor industry and preparation method thereof | |
| CN113151737B (en) | 08Ni3DR steel plate with hydrogen induced cracking resistance and manufacturing method thereof | |
| CN115323268B (en) | Gear steel with high strength and high toughness and capable of being used for induction quenching and manufacturing method thereof | |
| CN113549825B (en) | High-corrosion-resistance super stainless steel for ocean engineering equipment and manufacturing method thereof | |
| CN114086072B (en) | Boron-free medium-low nickel high-strength high-hardenability marine steel thick plate and preparation method thereof | |
| CN107955857B (en) | A kind of control nitrogen method during AOD smelting stainless steel | |
| CN109047694B (en) | Economic HIC-resistant pipeline steel plate X65MS for TMCP delivery and manufacturing method thereof | |
| CN117448691A (en) | Corrosion-resistant large-specification petroleum production and packaging spare steel and manufacturing method thereof | |
| CN116024504A (en) | Ferrite stainless steel for high-purity unstable electron special gas in semiconductor industry and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |