WO2024082324A1 - High-strength and high-toughness maraging stainless steel for ultralow-temperature engineering and manufacturing method therefor - Google Patents
High-strength and high-toughness maraging stainless steel for ultralow-temperature engineering and manufacturing method therefor Download PDFInfo
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- 239000010935 stainless steel Substances 0.000 title claims abstract description 66
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000012407 engineering method Methods 0.000 title 1
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- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
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- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000005242 forging Methods 0.000 claims description 40
- 230000032683 aging Effects 0.000 claims description 39
- 229910000734 martensite Inorganic materials 0.000 claims description 37
- 238000005266 casting Methods 0.000 claims description 21
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Definitions
- the invention relates to the technical field of maraging stainless steel, and in particular to a high-strength and high-toughness maraging stainless steel for ultra-low temperature engineering and a manufacturing method thereof.
- Martensitic aging stainless steel is a high-strength stainless steel with the superposition of two strengthening effects: low-carbon martensitic phase transformation strengthening and aging strengthening. It has ultra-high strength, good toughness, thermoplasticity, high-temperature hot forging, low hardening index and good weldability. It is now widely used in important fields such as aerospace, machinery manufacturing, and atomic energy. However, with the further development of the aviation industry, new service conditions have put forward higher requirements on the high strength and toughness, high corrosion resistance, and good processability of complex parts of the material, especially requiring the material to have higher ultra-low temperature (-196°C) impact toughness.
- the research on martensitic aging stainless steel at home and abroad is mainly focused on high strength performance, such as the martensitic aging stainless steel with ⁇ 0.2 ⁇ 1400MPa developed by the Iron and Steel Research Institute and the "high-strength and high-toughness martensitic aging stainless steel" disclosed in the Chinese patent application with application number CN 200710099335.3.
- this type of steel has no requirements for ultra-low temperature (-196°C) impact toughness.
- the S03 high-strength stainless steel (00Cr12Ni10MoTi martensitic aging stainless steel) developed abroad is mainly strengthened by Ti.
- practice shows that the impact toughness of this steel at ultra-low temperature is unstable.
- the Chinese patent application with application number 201811597240.9 discloses a "method for improving the low-temperature impact energy of 17-4PH martensitic aging stainless steel forgings based on organizational control", which is to reduce the total amount of high-temperature ferrite generated during the steel smelting process by optimizing the chemical composition, and then break the high-temperature ferrite in the smelting process by controlling the reasonable forging heating temperature and deformation amount and deformation direction.
- the long strip of high-temperature ferrite can be forged in a direction perpendicular to its length direction, upset it, and effectively eliminate its directionality.
- martensitic aging stainless steel adopts high chromium, high copper, low molybdenum components, and adds niobium, titanium, tantalum and other components, which are completely different from the composition and working principle of the martensitic aging stainless steel described in the present invention, and its low-temperature impact performance only achieves KV2 (-40°C) ⁇ 27J, and there is no record of the ultra-low temperature (-196°C) impact toughness of the steel.
- the Chinese patent application with application number 202010065551.1 discloses "a heat treatment method for improving the low-temperature impact toughness of 00Cr12Ni10MoTi martensitic aging stainless steel".
- the nickel and chromium contents in its martensitic aging stainless steel are close to those of the present invention, but the molybdenum content is much lower than that of the present invention, and the titanium content is much higher than that of the present invention; its heat treatment method includes a double solid solution heat treatment and an aging heat treatment arranged in sequence, wherein the double solid solution heat treatment includes three steps of pre-solution treatment, conventional solution treatment and water quenching treatment, and the low-temperature impact toughness also reaches AKv (-196°C): 90 ⁇ 140J.
- the heat treatment process of this technical solution is relatively cumbersome.
- the present invention has the advantages of a wide heat treatment process window, simple operation, strong controllability, high efficiency and low energy consumption.
- the invention provides a high-strength and high-toughness maraging stainless steel for ultra-low temperature engineering and a manufacturing method thereof.
- an appropriate amount of alloying element Mo is added to Cr and Ni stainless steel for alloying, while controlling the amount of Ti added to avoid the formation of large TiN and TiCN inclusions, and in combination with a suitable heat treatment process, fine and stable reverse transformation austenite is formed in the steel, so that the strength and toughness of the steel, especially the ultra-low temperature toughness, are significantly improved, and the comprehensive performance of the maraging stainless steel is greatly improved.
- a high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering comprising, by weight percentage: Cr 11.00%-13.00%, Ni 9.00%-11.00%, Mo 2.00%-4.00%, Ti ⁇ 0.05%, Al 0.001%-0.080%; harmful elements C ⁇ 0.03%, Si ⁇ 0.10%, Mn ⁇ 0.10%, P ⁇ 0.010%, S ⁇ 0.008%, [O] ⁇ 0.005%, [N] ⁇ 0.010%, [H] ⁇ 3ppm, Ca ⁇ 0.05%, Cu ⁇ 0.20%, As ⁇ 0.005%, Sn ⁇ 0.005%, Sb ⁇ 0.005%; the remainder is iron and unavoidable impurities.
- a method for manufacturing high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering comprising the following steps:
- the steel ingot or forging blank is homogenized at 1200°C ⁇ 15°C for more than 24 hours, forged or rolled into a plate or initial blank, and the initial forging temperature or rolling temperature is 1100 ⁇ 1200°C;
- step 1) the steel ingot or casting and forging blank is made of ultra-low carbon ultra-pure iron or high-purity alloy raw material, and the electrode rod is prepared by vacuum induction, and then obtained by electroslag remelting + vacuum consumable smelting.
- step 1) the steel ingot or casting and forging blank is made of ultra-low carbon ultra-pure iron or high-purity alloy raw material, refined by AOD or VOD, and the electrode rod is made by die casting or continuous casting, and then obtained by electroslag remelting + vacuum consumable smelting.
- the electrode rod is made and then subjected to vacuum consumable + electroslag remelting, or the electrode rod is made and then subjected to electroslag remelting + vacuum consumable + vacuum homogeneous composite blanking.
- the rolling ratio of the steel ingot is not less than 3, and the forging ratio of the forging blank is not less than 3.
- cooling is performed by water cooling, oil cooling or air cooling.
- the mechanical properties of the manufactured steel plate are: Rm ⁇ 950MPa, Re ⁇ 900MPa, A ⁇ 15%, Z ⁇ 60%, HV ⁇ 300, longitudinal Kv2 ⁇ 150J, transverse Kv2 ⁇ 100J, fatigue strength ⁇ -1 ⁇ 500MPa; the impact toughness at -196°C is: longitudinal Kv2 ⁇ 80J, transverse Kv2 ⁇ 55J.
- the present invention has the following beneficial effects:
- the ultra-low temperature engineering high-strength and high-toughness martensitic aging stainless steel of the present invention adopts a toughening design concept of replacing Ti with Mo, which makes the steel have better toughness while ensuring high strength, especially stable and excellent low-temperature impact toughness and good fatigue performance.
- the present invention is more suitable for the production of large castings and forgings, and mainly uses Mo to achieve the effect of strengthening and toughening, ensuring the homogenization and uniform and stable performance of large castings and forgings.
- Mo to achieve the effect of strengthening and toughening, ensuring the homogenization and uniform and stable performance of large castings and forgings.
- it avoids the difficulty of heat treatment and the instability of low-temperature impact performance caused by the serious macro-segregation of Ti in large castings and forgings; on the other hand, it also avoids the influence of the formation of large inclusions such as TiN and TiCN on fatigue performance.
- the present invention has a wide heat treatment process window for large castings and forgings, simple operation, strong controllability, high efficiency and low energy consumption;
- the present invention has broad application prospects in aerospace, marine engineering, energy engineering, etc.
- FIG. 1 is a rotational bending fatigue performance curve of high strength and high toughness maraging stainless steel for ultra-low temperature engineering in Example 1 of the present invention.
- FIG. 2 is a rotational bending fatigue performance curve of S03 steel in Comparative Example 1 of the present invention.
- the high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering described in the present invention comprises, by weight percentage, Cr 11.00% to 13.00%, Ni 9.00% to 11.00%, Mo 2.00% to 4.00%, Ti ⁇ 0.05%, Al 0.001% to 0.080%; harmful elements C ⁇ 0.03%, Si ⁇ 0.10%, Mn ⁇ 0.10%, P ⁇ 0.010%, S ⁇ 0.008%, [O] ⁇ 0.005%, [N] ⁇ 0.010%, [H] ⁇ 3ppm, Ca ⁇ 0.05%, Cu ⁇ 0.20%, As ⁇ 0.005%, Sn ⁇ 0.005%, Sb ⁇ 0.005%; the remainder is iron and unavoidable impurities.
- the method for manufacturing high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering of the present invention comprises the following steps:
- the steel ingot or forging blank is homogenized at 1200°C ⁇ 15°C for more than 24 hours, forged or rolled into a plate or initial blank, and the initial forging temperature or rolling temperature is 1100 ⁇ 1200°C;
- the steel ingot or casting and forging blank is made of ultra-low carbon ultra-pure iron or high-purity alloy raw material, and the electrode rod is prepared by vacuum induction, and then obtained by electroslag remelting + vacuum consumable smelting.
- step 1) the steel ingot or casting and forging blank is made of ultra-low carbon ultra-pure iron or high-purity alloy raw material, refined by AOD or VOD, and the electrode rod is made by die casting or continuous casting, and then obtained by electroslag remelting + vacuum consumable smelting.
- the electrode rod is made and then subjected to vacuum consumable + electroslag remelting, or the electrode rod is made and then subjected to electroslag remelting + vacuum consumable + vacuum homogeneous composite blanking.
- the rolling ratio of the steel ingot is not less than 3, and the forging ratio of the forging blank is not less than 3.
- cooling is performed by water cooling, oil cooling or air cooling.
- the mechanical properties of the manufactured steel plate are: Rm ⁇ 950MPa, Re ⁇ 900MPa, A ⁇ 15%, Z ⁇ 60%, HV ⁇ 300, longitudinal Kv2 ⁇ 150J, transverse Kv2 ⁇ 100J, fatigue strength ⁇ -1 ⁇ 500MPa; the impact toughness at -196°C is: longitudinal Kv2 ⁇ 80J, transverse Kv2 ⁇ 55J.
- the high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering described in the present invention adopts alloy component strengthening and toughening design, ultra-clean smelting process technology, and suitable heat treatment process technology to achieve microstructure regulation, thereby ensuring the high strength and high toughness of large castings and forgings and the stability and homogeneity of low-temperature performance.
- maraging stainless steel The alloy design reasons of the high-strength and high-toughness maraging stainless steel for ultra-low temperature engineering (hereinafter referred to as maraging stainless steel) described in the present invention are as follows:
- C in the maraging stainless steel of the present invention is not a strengthening element, but a harmful element.
- C easily forms intergranular precipitates with Cr, reducing its intergranular corrosion resistance;
- C can form large inclusions such as TiC or TiCN with elements such as Ti commonly found in maraging stainless steel, which harms the toughness of the steel. Therefore, the present invention strictly controls the carbon content in the maraging stainless steel, requiring it to be controlled below 0.03%, and the lower the better, taking into account the production cost.
- Si is not a strengthening element or a deoxidizing element in the maraging stainless steel of the present invention, and it is harmful to toughness. Therefore, the present invention controls Si ⁇ 0.10%, and the lower the better when considering the production cost.
- Mn Like Si, an increase in the Mn content in the maraging stainless steel of the present invention will harm the toughness of the steel. Therefore, the present invention controls Mn ⁇ 0.10%, and the lower the better, taking into account the production cost.
- Cr in the present invention plays a decisive role in corrosion resistance and also plays a strengthening role.
- Cr is a strong ferrite forming element and an element that reduces the austenite zone, which can reduce the Ms point.
- the present invention controls the Cr content between 11.0% and 13.0%.
- Ni in the present invention is an austenite-forming element, which is crucial for expanding the austenite stable region, lowering the Ms point, and balancing with the Cr equivalent content to form the M+A dual-phase region falling within the Schaeffler equilibrium phase diagram.
- Ni also has the effects of solid solution strengthening and aging strengthening. It precipitates nano-scale Ni 3 Mo, Ni 3 Al, Ni 3 Ti and other strengthening phases with Mo, Al, and Ti during aging to achieve high strength; Ni is also the main element for maintaining low-temperature toughness in steel. Therefore, the Ni content in the present invention is controlled at 9.00% to 11.00%.
- Mo The present invention makes full use of the toughening and corrosion resistance-enhancing effects of Mo.
- Mo can lower the Ms point and expand the austenite stable zone, which is beneficial to obtain a certain amount of residual austenite in maraging stainless steel and ensure the low-temperature toughness of the steel.
- Mo can also play a role in solid solution strengthening in maraging stainless steel, and react with Ni to precipitate nano-scale Ni 3 Mo strengthening phases through aging, exerting its significant strengthening effect.
- the alloying element Mo in maraging stainless steel can also prevent the precipitation phase from precipitating along the original austenite grain boundaries, thereby avoiding intergranular fracture and improving fracture toughness.
- the Mo content is controlled within the range of 2.0% to 4.0%.
- Ti is one of the most effective ageing strengthening alloying elements in martensitic aging stainless steel. Ti and Ni age and precipitate nano-scale Ni 3 Ti strengthening phases, which can greatly improve the strength of steel. However, Ti weakens or even harms the toughness of martensitic aging stainless steel. Although adding a small amount of Ti can significantly increase the strength of steel, the toughness will decrease significantly. The significant effect of Ti on strength and toughness has been verified in the similar martensitic aging stainless steel S03. Since Ti is an element that is easy to segregate in steel, a small amount of segregation can have a significant impact on strength and toughness.
- the low-temperature toughness at -196°C can be sharply reduced from more than 80J to less than 30J, resulting in unqualified performance.
- macro segregation is difficult to avoid or eliminate.
- Ti is used for strengthening, it is very easy to cause unqualified performance of large forgings, and the corresponding heat treatment process window is very narrow, which causes great difficulties for engineering applications, and even cannot achieve engineering applications.
- Ti is easy to combine with harmful elements C, S, and N in maraging stainless steel to form inclusions such as TiN, TiCN, and TiCS.
- the present invention abandons the strengthening effect of Ti and makes full use of the strengthening and toughening effect of Mo. Since the C content in maraging stainless steel is generally controlled within the order of 100ppm, the intergranular corrosion problem is also basically eliminated. Therefore, the present invention controls the Ti content to be below 0.05%.
- Al usually added as a deoxidizer in steel. To ensure that the steel in the present invention is fully deoxidized, the Al content is controlled within 0.080%.
- the maraging stainless steel of the present invention is ultra-low temperature engineering steel.
- harmful elements in the steel must be strictly controlled.
- the present invention requires that the harmful elements in the steel be controlled within the following ranges, and the lower the better in consideration of production costs: P ⁇ 0.010%, S ⁇ 0.008%, [O] ⁇ 0.005%, [N] ⁇ 0.010%, [H] ⁇ 3ppm, As, Sn, Sb are controlled below 0.005% respectively, Cu ⁇ 0.20%, Ca ⁇ 0.05%.
- a high-strength and high-toughness martensitic aged stainless steel ingot is smelted in a 50kg vacuum induction furnace, and the composition is shown in Table 1.
- the alloy composition is designed with Mo as the main strengthening element, and the Mo content is increased to 2.52%; the strengthening effect of Ti is abandoned, and the Ti content is reduced to less than 0.01%; the Al content is added as a deoxidizer and controlled at 0.05%.
- Other harmful elements C, Si, Mn, P, and S are all controlled at a low level.
- the steel ingot is subjected to high temperature homogenization diffusion annealing at 1200°C ⁇ 24h, forged into a square billet with a cross-sectional size of 80mm ⁇ 80mm, and then processed into a performance sample billet, and then processed into performance samples and metallographic samples after solution treatment and aging treatment.
- the mechanical property test is carried out in accordance with the requirements of GB/T228 "Metallic Materials Room Temperature Tensile Test Method” and GB/T229 “Metallic Materials Charpy Pendulum Impact Test Method”.
- the fatigue performance is tested according to GB T 4337-2015 "Metallic Materials Fatigue Test Rotational Bending Method” to test the cylindrical rotational bending fatigue performance, and the experiment is carried out on a PQ1-6 pure bending fatigue testing machine.
- the mechanical properties test results of the steel in this embodiment are shown in Table 2.
- the room temperature tensile strength Rm and yield strength R0.2 are greater than 1000MPa and 950MPa respectively
- the room temperature impact toughness is greater than 160J
- the -196°C impact toughness is greater than 100J.
- the room temperature fatigue strength ⁇ -1 is greater than 565MPa
- the fatigue SN curve is shown in Figure 1.
- the high-strength and high-toughness martensitic aged stainless steel of the present invention can obtain good strength and low-temperature toughness in a wide range of heat treatment processes, and the heat treatment process of Example 1 in Table 2 is only a typical representative thereof.
- a high-strength and high-toughness martensitic aged stainless steel ingot is smelted in a 50kg vacuum induction furnace, and the composition is shown in Example 2 in Table 1.
- the alloy composition is designed with Mo as the main strengthening element, and the Mo content is increased to 3.90%; the strengthening effect of Ti is abandoned, and the Ti content is reduced to 0.04%; the Al content is added as a deoxidizer and controlled at 0.07%.
- Other harmful elements C, Si, Mn, P, and S are all controlled at a low level.
- the steel ingot is subjected to high temperature homogenization diffusion annealing at 1200°C ⁇ 24h, forged into a square billet with a cross-sectional size of 80mm ⁇ 80mm, and then processed into a performance sample billet, and then processed into performance samples and metallographic samples after solution treatment and aging treatment.
- the mechanical property test is carried out in accordance with the requirements of GB/T228 "Metallic Materials Room Temperature Tensile Test Method” and GB/T229 “Metallic Materials Charpy Pendulum Impact Test Method”.
- the fatigue performance is tested according to GB T 4337-2015 "Metallic Materials Fatigue Test Rotational Bending Method” to test the cylindrical rotational bending fatigue performance, and the experiment is carried out on a PQ1-6 pure bending fatigue testing machine.
- the mechanical property test results of the steel in this embodiment are shown in Table 2.
- the room temperature tensile strength Rm and yield strength R0.2 are greater than 1150MPa and 1080MPa respectively
- the room temperature impact toughness is greater than 150J
- the -196°C impact toughness is greater than 90J
- the room temperature fatigue strength ⁇ -1 is greater than 580MPa.
- the high-strength and high-toughness martensitic aged stainless steel of the present invention can obtain good strength and low-temperature toughness in a wide range of heat treatment processes, and the heat treatment process of Example 2 in Table 2 is only a typical representative thereof.
- a high-strength and high-toughness martensitic aged stainless steel ingot is smelted in a 50kg vacuum induction furnace, and the composition is shown in Table 1.
- the alloy composition is designed with Mo as the main strengthening element, and the Mo content is increased to 2.10%; the strengthening effect of Ti is abandoned, and the residual Ti content is reduced to 0.002%; the Al content is added as a deoxidizer and controlled at 0.015%.
- Other harmful elements C, Si, Mn, P, and S are all controlled at a low level.
- the steel ingot is subjected to high temperature homogenization diffusion annealing at 1200°C ⁇ 24h, forged into a square billet with a cross-sectional size of 80mm ⁇ 80mm, and then processed into a performance sample billet, and then processed into performance samples and metallographic samples after solution treatment and aging treatment.
- the mechanical property test is carried out in accordance with the requirements of GB/T228 "Metallic Materials Room Temperature Tensile Test Method” and GB/T229 “Metallic Materials Charpy Pendulum Impact Test Method”.
- the fatigue performance is tested according to GB T 4337-2015 "Metallic Materials Fatigue Test Rotational Bending Method” to test the cylindrical rotational bending fatigue performance, and the experiment is carried out on a PQ1-6 pure bending fatigue testing machine.
- the mechanical property test results of the steel in this embodiment are shown in Table 2.
- the room temperature tensile strength Rm and yield strength R0.2 are greater than 950MPa and 905MPa respectively
- the room temperature impact toughness is greater than 175J
- the -196°C impact toughness is greater than 120J
- the room temperature fatigue strength ⁇ -1 is greater than 540MPa.
- the high-strength and high-toughness martensitic aged stainless steel of the present invention can obtain good strength and low-temperature toughness in a wide range of heat treatment processes, and the heat treatment process of Example 3 in Table 2 is only a typical representative thereof.
- This comparative example adopts a 50kg vacuum induction furnace to smelt martensitic aging stainless steel S03 steel, and the composition is shown in Table 1.
- the alloy components Cr, Ni, and Mo are all controlled according to the upper limit range of S03 steel.
- the Mo content is reduced to 0.71%, and the Ti content is increased to 0.16%, that is, Ti is mainly used as a strengthening element, and Al is used as a deoxidizer, and its content is controlled at 0.02%, and other harmful elements C, Si, Mn, P, and S are all controlled at a relatively low level.
- the steel ingot is subjected to high temperature homogenization diffusion annealing at 1200°C ⁇ 24h, forged into a square billet with a cross-sectional size of 80mm ⁇ 80mm, processed into a performance sample billet, and then processed into performance samples and metallographic samples after solution treatment and aging treatment.
- the room temperature tensile strength Rm and yield strength R0.2 of S03 steel are slightly higher than those in Example 1, reaching more than 1000MPa, but its yield strength ratio is very high and its plasticity is poor.
- the room temperature impact toughness is slightly better than that in Example 1, reaching more than 170J, but the impact toughness is significantly deteriorated and extremely unstable at -196°C.
- the impact energy of the first heat treatment method is only 46J, and the impact energy of the second heat treatment method is the same as that of Example 1. It is also difficult to change this phenomenon by using other heat treatment processes.
- the room temperature fatigue strength of the sample with the best strength and toughness combination reached 505 MPa, and the fatigue S-N curve is shown in Figure 2.
- the room temperature fatigue strength is significantly lower (60 MPa lower) than that of Example 1.
- the heat treatment process window of this comparative example is significantly narrower than that of Example 1, which causes certain difficulties for engineering heat treatment.
- a 50kg vacuum induction furnace is used to smelt martensitic aging stainless steel S03 steel, and the composition is shown in Table 1.
- the alloy components Cr, Ni, and Mo are all controlled according to the upper limit range of S03 steel.
- the Mo content is reduced to 0.71%, and Ti is used as the main strengthening element to further increase its content to reach the upper limit of the control range of 0.25%.
- Al is used as a deoxidizer and its content is controlled at 0.06%, and other harmful elements C, Si, Mn, P, and S are all controlled at a relatively low level.
- the steel ingot is subjected to high temperature homogenization diffusion annealing at 1200°C ⁇ 24h, forged into a square billet with a cross-sectional size of 80mm ⁇ 80mm, processed into a performance sample billet, and then processed into performance samples and metallographic samples after solution treatment and aging treatment.
- the room temperature tensile strength Rm and yield strength R 0.2 of S03 steel fluctuate greatly, ranging from 900 to 1100MPa, the plasticity is very low, and the room temperature impact toughness is lower than that of Example 1 and Comparative Example 1.
- the impact toughness deteriorates significantly at -196°C, with a maximum of only 37J, and other heat treatment processes cannot improve its low temperature toughness.
- the ultra-low temperature engineering high-strength and high-toughness martensitic aging stainless steel of the present invention has good and stable strength-toughness matching compared with conventional S03 steel, both at room temperature and low temperature, and its fatigue performance is significantly better than that of S03 steel, and its heat treatment process window is wide, so it is particularly suitable for the production of large castings and forgings required for large equipment, and has broad application prospects in aerospace, marine engineering, energy engineering and the like.
Abstract
A high-strength and high-toughness maraging stainless steel for ultralow-temperature engineering and a manufacturing method therefor. The main components in the steel comprise: 11.00%-13.00% of Cr, 9.00%-11.00% of Ni, 2.00%-4.00% of Mo, Ti less than or equal to 0.05%, 0.001%-0.080% of Al, and the balance of iron, harmful elements, and impurities; the tensile strength at a room temperature is larger than or equal to 950 MPa, the yield strength is larger than or equal to 900 MPa, the impact toughness Kv2 at the room temperature is larger than or equal to 150 J, and the impact toughness Kv2 at -196°C is larger than or equal to 80 J. The ratio of chemical components in the maraging stainless steel is optimized, a proper amount of alloying element Mo is added on the basis of Cr and Ni stainless steel for alloying, and the addition amount of Ti is controlled to avoid the formation of large-sized TiN and TiCN inclusions, fine and stable reversed austenite is formed in the steel in cooperation with a proper heat treatment process, so that the toughness of the steel, especially the ultralow-temperature toughness, is remarkably improved, and the comprehensive performance of the maraging stainless steel is greatly improved.
Description
本发明涉及马氏体时效不锈钢技术领域，尤其涉及一种超低温工程用高强高韧马氏体时效不锈钢及其制造方法。The invention relates to the technical field of maraging stainless steel, and in particular to a high-strength and high-toughness maraging stainless steel for ultra-low temperature engineering and a manufacturing method thereof.
马氏体时效不锈钢是由低碳马氏体相变强化和时效强化两种强化效应叠加的高强度不锈钢，具有超高强度、良好的韧性、热塑性、高温热锻性、低的硬化指数和良好的焊接性，现已广泛应用于航空航天、机械制造、原子能等重要领域。然而，随着航空工业的进一步发展，新的服役条件对材料的高强高韧性、高耐蚀性、复杂零件的良好加工性等方面提出了更高的要求，尤其是要求材料具有更高的超低温(-196℃)冲击韧性。Martensitic aging stainless steel is a high-strength stainless steel with the superposition of two strengthening effects: low-carbon martensitic phase transformation strengthening and aging strengthening. It has ultra-high strength, good toughness, thermoplasticity, high-temperature hot forging, low hardening index and good weldability. It is now widely used in important fields such as aerospace, machinery manufacturing, and atomic energy. However, with the further development of the aviation industry, new service conditions have put forward higher requirements on the high strength and toughness, high corrosion resistance, and good processability of complex parts of the material, especially requiring the material to have higher ultra-low temperature (-196℃) impact toughness.
目前国内外对马氏体时效不锈钢的研究主要集中在高强度性能上，如钢铁研究总院开发的σ
0.2≥1400MPa的马氏体时效不锈钢、申请号为CN 200710099335.3的中国专利申请公开的“高强高韧马氏体时效不锈钢”。但是这类钢对超低温(-196℃)冲击韧性方面没有要求。国外研发的S03高强度不锈钢(00Cr12Ni10MoTi马氏体时效不锈钢)主要采用是Ti强化，然而实践表明，该钢种在超低温下的冲击韧性不稳定，其原因是Ti的微量变化或偏析即可引起相变温度的巨大波动。为保证低温强韧性而采用的热处理工艺过程复杂且温度窗口很窄，对于大型铸锻件来说，不仅生产工艺复杂不易操作、可控性差、能源消耗大，而且因Ti的凝固偏析严重导致大型锻件无法保证均质化及性能的均匀和稳定。此外，由于高Ti强化，Ti易于N、C结合形成TiN、TiCN等大型夹杂物，严重降低了大型锻件的疲劳性能。
At present, the research on martensitic aging stainless steel at home and abroad is mainly focused on high strength performance, such as the martensitic aging stainless steel with σ 0.2 ≥1400MPa developed by the Iron and Steel Research Institute and the "high-strength and high-toughness martensitic aging stainless steel" disclosed in the Chinese patent application with application number CN 200710099335.3. However, this type of steel has no requirements for ultra-low temperature (-196℃) impact toughness. The S03 high-strength stainless steel (00Cr12Ni10MoTi martensitic aging stainless steel) developed abroad is mainly strengthened by Ti. However, practice shows that the impact toughness of this steel at ultra-low temperature is unstable. The reason is that a slight change or segregation of Ti can cause a huge fluctuation in the phase transition temperature. The heat treatment process used to ensure low-temperature strength and toughness is complex and the temperature window is very narrow. For large castings and forgings, not only is the production process complex and difficult to operate, the controllability is poor, and the energy consumption is large, but also due to the serious solidification segregation of Ti, large forgings cannot guarantee homogenization and uniform and stable performance. In addition, due to high Ti strengthening, Ti is easy to combine with N and C to form large inclusions such as TiN and TiCN, which seriously reduces the fatigue performance of large forgings.
申请号为201811597240.9的中国专利申请公开了一种“基于组织控制提高17-4PH马氏体时效不锈钢锻件低温冲击功的方法”，是通过化学成分优化，减少钢材冶炼过程中生成的高温铁素体总量，再通过控制合理的锻造加热温度和变形量及变形方向将冶炼过程中的高温铁素体打碎，长条状高温铁素体可通过沿着与其长度方向垂直的方向进行锻造，将其镦粗，有效消除其方向性，最后再经过两次固溶+时效热处理，在再结晶过程中将细小的高温铁素体进一步消除，提高低温冲击功。其马氏体时效不锈钢采用了高铬、高铜、低 钼成分，并且添加了铌、钛、钽等成分，与本发明所述马氏体时效不锈钢的成分组成及作用原理完全不同，并且其仅低温冲击性能仅实现了KV2(-40℃)≥27J，没有记载钢的超低温(-196℃)冲击韧性。The Chinese patent application with application number 201811597240.9 discloses a "method for improving the low-temperature impact energy of 17-4PH martensitic aging stainless steel forgings based on organizational control", which is to reduce the total amount of high-temperature ferrite generated during the steel smelting process by optimizing the chemical composition, and then break the high-temperature ferrite in the smelting process by controlling the reasonable forging heating temperature and deformation amount and deformation direction. The long strip of high-temperature ferrite can be forged in a direction perpendicular to its length direction, upset it, and effectively eliminate its directionality. Finally, after two solid solution + aging heat treatments, the fine high-temperature ferrite is further eliminated during the recrystallization process to improve the low-temperature impact energy. Its martensitic aging stainless steel adopts high chromium, high copper, low molybdenum components, and adds niobium, titanium, tantalum and other components, which are completely different from the composition and working principle of the martensitic aging stainless steel described in the present invention, and its low-temperature impact performance only achieves KV2 (-40℃) ≥ 27J, and there is no record of the ultra-low temperature (-196℃) impact toughness of the steel.
申请号为202010065551.1的中国专利申请公开了“一种提升00Cr12Ni10MoTi马氏体时效不锈钢低温冲击韧性的热处理方法”，其马氏体时效不锈钢中的镍、铬含量与本发明接近，但钼含量远低于本发明，钛含量远高于本发明；其热处理方法包括按顺序设置的双固溶热处理和时效热处理，其中双固溶热处理包括预固溶处理、常规固溶处理和水淬处理工序三个步骤，低温冲击韧性也达到了AKv(-196℃):90～140J。但是该技术方案的热处理工艺较为繁琐，本发明与其相比，具有热处理工艺窗口宽、操作简单，可控性强，效率高、能耗低的优点。The Chinese patent application with application number 202010065551.1 discloses "a heat treatment method for improving the low-temperature impact toughness of 00Cr12Ni10MoTi martensitic aging stainless steel". The nickel and chromium contents in its martensitic aging stainless steel are close to those of the present invention, but the molybdenum content is much lower than that of the present invention, and the titanium content is much higher than that of the present invention; its heat treatment method includes a double solid solution heat treatment and an aging heat treatment arranged in sequence, wherein the double solid solution heat treatment includes three steps of pre-solution treatment, conventional solution treatment and water quenching treatment, and the low-temperature impact toughness also reaches AKv (-196°C): 90~140J. However, the heat treatment process of this technical solution is relatively cumbersome. Compared with it, the present invention has the advantages of a wide heat treatment process window, simple operation, strong controllability, high efficiency and low energy consumption.
发明内容Summary of the invention
本发明提供了一种超低温工程用高强高韧马氏体时效不锈钢及其制造方法，通过优化马氏体时效不锈钢的化学成分配比，在Cr、Ni不锈钢的基础上添加适量的合金化元素Mo进行合金化，同时控制Ti的添加量以避免大型TiN、TiCN夹杂物的形成，配合适宜的热处理工艺，在钢中形成细小稳定的逆转变奥氏体，使钢的强韧性尤其是超低温韧性得到显著提高，大幅度提高了马氏体时效不锈钢的综合性能。The invention provides a high-strength and high-toughness maraging stainless steel for ultra-low temperature engineering and a manufacturing method thereof. By optimizing the chemical composition ratio of the maraging stainless steel, an appropriate amount of alloying element Mo is added to Cr and Ni stainless steel for alloying, while controlling the amount of Ti added to avoid the formation of large TiN and TiCN inclusions, and in combination with a suitable heat treatment process, fine and stable reverse transformation austenite is formed in the steel, so that the strength and toughness of the steel, especially the ultra-low temperature toughness, are significantly improved, and the comprehensive performance of the maraging stainless steel is greatly improved.
为了达到上述目的，本发明采用以下技术方案实现：In order to achieve the above object, the present invention adopts the following technical solutions:
一种超低温工程用高强高韧马氏体时效不锈钢，按重量百分比计，其成分包括：Cr 11.00％～13.00％，Ni 9.00％～11.00％，Mo 2.00％～4.00％，Ti≤0.05％，Al 0.001％～0.080％；钢中有害元素C≤0.03％，Si≤0.10％，Mn≤0.10％，P≤0.010％，S≤0.008％，[O]≤0.005％，[N]≤0.010％，[H]≤3ppm，Ca≤0.05％，Cu≤0.20％，As≤0.005％，Sn≤0.005％，Sb≤0.005％；余量为铁和不可避免的杂质。A high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering, comprising, by weight percentage: Cr 11.00%-13.00%, Ni 9.00%-11.00%, Mo 2.00%-4.00%, Ti≤0.05%, Al 0.001%-0.080%; harmful elements C≤0.03%, Si≤0.10%, Mn≤0.10%, P≤0.010%, S≤0.008%, [O]≤0.005%, [N]≤0.010%, [H]≤3ppm, Ca≤0.05%, Cu≤0.20%, As≤0.005%, Sn≤0.005%, Sb≤0.005%; the remainder is iron and unavoidable impurities.
一种超低温工程用高强高韧马氏体时效不锈钢的制造方法，包括如下步骤：A method for manufacturing high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering, comprising the following steps:
1)制备钢锭或铸锻件坯料；1) Prepare steel ingots or casting and forging blanks;
2)热加工：钢锭或锻件坯料于1200℃±15℃均匀化处理24小时以上，锻造或轧制成板材或初始坯料，始锻温度或开轧温度为1100～1200℃；2) Hot working: The steel ingot or forging blank is homogenized at 1200℃±15℃ for more than 24 hours, forged or rolled into a plate or initial blank, and the initial forging temperature or rolling temperature is 1100～1200℃;
3)一次固溶处理：600～800℃保温2～14小时，冷却至室温；3) Primary solution treatment: 600-800℃ for 2-14 hours, then cool to room temperature;
4)时效处理：450～550℃保温2～20小时，空冷至室温。4) Aging treatment: keep at 450-550℃ for 2-20 hours, and air cool to room temperature.
进一步的，所述步骤1)中，钢锭或铸锻件坯料采用超低碳超纯铁或高纯合金原料， 经真空感应制取电极棒，然后经电渣重熔+真空自耗冶炼获得。Furthermore, in step 1), the steel ingot or casting and forging blank is made of ultra-low carbon ultra-pure iron or high-purity alloy raw material, and the electrode rod is prepared by vacuum induction, and then obtained by electroslag remelting + vacuum consumable smelting.
进一步的，所述步骤1)中，钢锭或铸锻件坯料采用超低碳超纯铁或高纯合金原料，经AOD或VOD精炼，采用模铸或连铸制取电极棒，然后经电渣重熔+真空自耗冶炼获得。Furthermore, in step 1), the steel ingot or casting and forging blank is made of ultra-low carbon ultra-pure iron or high-purity alloy raw material, refined by AOD or VOD, and the electrode rod is made by die casting or continuous casting, and then obtained by electroslag remelting + vacuum consumable smelting.
进一步的，所述钢锭或铸锻件坯料的重量大于20吨时，制取电极棒后经真空自耗+电渣重熔获得，或制取电极棒后经电渣重熔+真空自耗+真空同质复合制坯获得。Furthermore, when the weight of the steel ingot or casting and forging blank is greater than 20 tons, the electrode rod is made and then subjected to vacuum consumable + electroslag remelting, or the electrode rod is made and then subjected to electroslag remelting + vacuum consumable + vacuum homogeneous composite blanking.
进一步的，所述步骤2)中，钢锭的轧制比不小于3，锻件坯料的锻造比不小于3。Furthermore, in the step 2), the rolling ratio of the steel ingot is not less than 3, and the forging ratio of the forging blank is not less than 3.
进一步的，所述步骤3)中，冷却采用水冷、油冷或空冷。Furthermore, in step 3), cooling is performed by water cooling, oil cooling or air cooling.
进一步的，所制造的钢板力学性能为：Rm≥950MPa，Re≥900MPa，A≥15％，Z≥60％，HV≥300，纵向Kv2≥150J，横向Kv2≥100J，疲劳强度σ
-1≥500MPa；-196℃的冲击韧性为：纵向Kv2≥80J，横向Kv2≥55J。
Furthermore, the mechanical properties of the manufactured steel plate are: Rm≥950MPa, Re≥900MPa, A≥15%, Z≥60%, HV≥300, longitudinal Kv2≥150J, transverse Kv2≥100J, fatigue strength σ -1 ≥500MPa; the impact toughness at -196°C is: longitudinal Kv2≥80J, transverse Kv2≥55J.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the present invention has the following beneficial effects:
1)本发明所述超低温工程用高强高韧马氏体时效不锈钢采用以Mo替Ti的强韧化设计理念，在保证高强度的基础上，使钢具有更好的强韧性，尤其是具有稳定、优良的低温冲击韧性和良好的疲劳性能。1) The ultra-low temperature engineering high-strength and high-toughness martensitic aging stainless steel of the present invention adopts a toughening design concept of replacing Ti with Mo, which makes the steel have better toughness while ensuring high strength, especially stable and excellent low-temperature impact toughness and good fatigue performance.
2)本发明更适用于大型铸锻件的生产，以Mo为主实现强韧化的作用，确保大型铸锻件的均质化和性能的均匀稳定，一方面避免了Ti在大型铸锻件中因易形成严重的宏观偏析而造成热处理困难和低温冲击性能的不稳定；另一方面也避免了TiN、TiCN大型夹杂物的形成对疲劳性能的影响。2) The present invention is more suitable for the production of large castings and forgings, and mainly uses Mo to achieve the effect of strengthening and toughening, ensuring the homogenization and uniform and stable performance of large castings and forgings. On the one hand, it avoids the difficulty of heat treatment and the instability of low-temperature impact performance caused by the serious macro-segregation of Ti in large castings and forgings; on the other hand, it also avoids the influence of the formation of large inclusions such as TiN and TiCN on fatigue performance.
3)本发明对大型铸锻件而言热处理工艺窗口宽、操作简单、可控性强、效率高、能耗低；3) The present invention has a wide heat treatment process window for large castings and forgings, simple operation, strong controllability, high efficiency and low energy consumption;
4)本发明在航空航天、海洋工程、能源工程等方面均具有广泛的应用前景。4) The present invention has broad application prospects in aerospace, marine engineering, energy engineering, etc.
图1是本发明实施例1中超低温工程用高强高韧马氏体时效不锈钢的旋转弯曲疲劳性能曲线。FIG. 1 is a rotational bending fatigue performance curve of high strength and high toughness maraging stainless steel for ultra-low temperature engineering in Example 1 of the present invention.
图2是本发明对比例1中S03钢的旋转弯曲疲劳性能曲线。FIG. 2 is a rotational bending fatigue performance curve of S03 steel in Comparative Example 1 of the present invention.
本发明所述一种超低温工程用高强高韧马氏体时效不锈钢，按重量百分比计，其成分包括：Cr 11.00％～13.00％，Ni 9.00％～11.00％，Mo 2.00％～4.00％，Ti≤0.05％，Al 0.001％～0.080％；钢中有害元素C≤0.03％，Si≤0.10％，Mn≤0.10％，P≤0.010％，S≤0.008％，[O] ≤0.005％，[N]≤0.010％，[H]≤3ppm，Ca≤0.05％，Cu≤0.20％，As≤0.005％，Sn≤0.005％，Sb≤0.005％；余量为铁和不可避免的杂质。The high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering described in the present invention comprises, by weight percentage, Cr 11.00% to 13.00%, Ni 9.00% to 11.00%, Mo 2.00% to 4.00%, Ti≤0.05%, Al 0.001% to 0.080%; harmful elements C≤0.03%, Si≤0.10%, Mn≤0.10%, P≤0.010%, S≤0.008%, [O]≤0.005%, [N]≤0.010%, [H]≤3ppm, Ca≤0.05%, Cu≤0.20%, As≤0.005%, Sn≤0.005%, Sb≤0.005%; the remainder is iron and unavoidable impurities.
本发明所述一种超低温工程用高强高韧马氏体时效不锈钢的制造方法，包括如下步骤：The method for manufacturing high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering of the present invention comprises the following steps:
1)制备钢锭或铸锻件坯料；1) Prepare steel ingots or casting and forging blanks;
2)热加工：钢锭或锻件坯料于1200℃±15℃均匀化处理24小时以上，锻造或轧制成板材或初始坯料，始锻温度或开轧温度为1100～1200℃；2) Hot working: The steel ingot or forging blank is homogenized at 1200℃±15℃ for more than 24 hours, forged or rolled into a plate or initial blank, and the initial forging temperature or rolling temperature is 1100～1200℃;
3)一次固溶处理：600～800℃保温2～14小时，冷却至室温；3) Primary solution treatment: 600-800℃ for 2-14 hours, then cool to room temperature;
4)时效处理：450～550℃保温2～20小时，空冷至室温。4) Aging treatment: keep at 450-550℃ for 2-20 hours, and air cool to room temperature.
进一步的，所述步骤1)中，钢锭或铸锻件坯料采用超低碳超纯铁或高纯合金原料，经真空感应制取电极棒，然后经电渣重熔+真空自耗冶炼获得。Furthermore, in the step 1), the steel ingot or casting and forging blank is made of ultra-low carbon ultra-pure iron or high-purity alloy raw material, and the electrode rod is prepared by vacuum induction, and then obtained by electroslag remelting + vacuum consumable smelting.
进一步的，所述步骤1)中，钢锭或铸锻件坯料采用超低碳超纯铁或高纯合金原料，经AOD或VOD精炼，采用模铸或连铸制取电极棒，然后经电渣重熔+真空自耗冶炼获得。Furthermore, in step 1), the steel ingot or casting and forging blank is made of ultra-low carbon ultra-pure iron or high-purity alloy raw material, refined by AOD or VOD, and the electrode rod is made by die casting or continuous casting, and then obtained by electroslag remelting + vacuum consumable smelting.
进一步的，所述钢锭或铸锻件坯料的重量大于20吨时，制取电极棒后经真空自耗+电渣重熔获得，或制取电极棒后经电渣重熔+真空自耗+真空同质复合制坯获得。Furthermore, when the weight of the steel ingot or casting and forging blank is greater than 20 tons, the electrode rod is made and then subjected to vacuum consumable + electroslag remelting, or the electrode rod is made and then subjected to electroslag remelting + vacuum consumable + vacuum homogeneous composite blanking.
进一步的，所述步骤2)中，钢锭的轧制比不小于3，锻件坯料的锻造比不小于3。Furthermore, in the step 2), the rolling ratio of the steel ingot is not less than 3, and the forging ratio of the forging blank is not less than 3.
进一步的，所述步骤3)中，冷却采用水冷、油冷或空冷。Furthermore, in step 3), cooling is performed by water cooling, oil cooling or air cooling.
进一步的，所制造的钢板力学性能为：Rm≥950MPa，Re≥900MPa，A≥15％，Z≥60％，HV≥300，纵向Kv2≥150J，横向Kv2≥100J，疲劳强度σ
-1≥500MPa；-196℃的冲击韧性为：纵向Kv2≥80J，横向Kv2≥55J。
Furthermore, the mechanical properties of the manufactured steel plate are: Rm≥950MPa, Re≥900MPa, A≥15%, Z≥60%, HV≥300, longitudinal Kv2≥150J, transverse Kv2≥100J, fatigue strength σ -1 ≥500MPa; the impact toughness at -196°C is: longitudinal Kv2≥80J, transverse Kv2≥55J.
本发明所述一种超低温工程用高强高韧马氏体时效不锈钢采用合金成分强韧化设计及超洁净化冶炼工艺技术、适合的热处理工艺技术实现微观组织调控，保证了大型铸锻件的高强高韧性及低温性能的稳定性、均质性。The high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering described in the present invention adopts alloy component strengthening and toughening design, ultra-clean smelting process technology, and suitable heat treatment process technology to achieve microstructure regulation, thereby ensuring the high strength and high toughness of large castings and forgings and the stability and homogeneity of low-temperature performance.
本发明所述一种超低温工程用高强高韧马氏体时效不锈钢(以下简称马氏体时效不锈钢)的合金设计理由如下：The alloy design reasons of the high-strength and high-toughness maraging stainless steel for ultra-low temperature engineering (hereinafter referred to as maraging stainless steel) described in the present invention are as follows:
C：本发明所述马氏体时效不锈钢中C不是强化元素，而是有害元素。一方面，C易与Cr形成晶间析出物，降低其抗晶间腐蚀性能；另一方面，C可与马氏体时效不锈钢中常见的Ti等元素形成TiC或TiCN等大型夹杂物，危害钢的韧性。因此本发明严格控制马氏体 时效不锈钢中的碳含量，要求控制在0.03％以下，且在综合考虑生产成本的情况下越低越好。C: C in the maraging stainless steel of the present invention is not a strengthening element, but a harmful element. On the one hand, C easily forms intergranular precipitates with Cr, reducing its intergranular corrosion resistance; on the other hand, C can form large inclusions such as TiC or TiCN with elements such as Ti commonly found in maraging stainless steel, which harms the toughness of the steel. Therefore, the present invention strictly controls the carbon content in the maraging stainless steel, requiring it to be controlled below 0.03%, and the lower the better, taking into account the production cost.
Si：在本发明所述马氏体时效不锈钢中Si不是强化元素或脱氧元素，且对韧性造成危害。因此，本发明控制Si≤0.10％，且在综合考虑生产成本的情况下越低越好。Si: Si is not a strengthening element or a deoxidizing element in the maraging stainless steel of the present invention, and it is harmful to toughness. Therefore, the present invention controls Si≤0.10%, and the lower the better when considering the production cost.
Mn：与Si一样，在本发明所述马氏体时效不锈钢中Mn含量的升高将危害钢的韧性，因此，本发明控制Mn≤0.10％，且在综合考虑生产成本的情况下越低越好。Mn: Like Si, an increase in the Mn content in the maraging stainless steel of the present invention will harm the toughness of the steel. Therefore, the present invention controls Mn≤0.10%, and the lower the better, taking into account the production cost.
Cr：本发明中Cr对耐蚀性起着决定性作用，同时也起着强化作用。Cr是强铁素体形成元素和缩小奥氏体区元素，能够降低Ms点。选择Cr含量控制范围时既要考虑耐蚀性要求，也要考虑其与Ni等元素的平衡，确保Ni、Cr当量含量落入舍弗勒平衡相图的M+A双相区范围内，因此本发明将Cr含量控制在11.0％～13.0％之间。Cr: Cr in the present invention plays a decisive role in corrosion resistance and also plays a strengthening role. Cr is a strong ferrite forming element and an element that reduces the austenite zone, which can reduce the Ms point. When selecting the Cr content control range, it is necessary to consider both the corrosion resistance requirements and its balance with elements such as Ni to ensure that the Ni and Cr equivalent contents fall within the M+A dual-phase region of the Schaeffler equilibrium phase diagram. Therefore, the present invention controls the Cr content between 11.0% and 13.0%.
Ni：本发明中Ni作为奥氏体相形成元素，对于扩大奥氏体稳定区、降低Ms点，并与Cr当量含量平衡以形成落入舍弗勒平衡相图的M+A双相区范围内至关重要。此外，Ni还有固溶强化和时效强化的作用，其与Mo、Al、Ti时效析出纳米级Ni
3Mo、Ni
3Al、Ni
3Ti等强化相，以此达到高强度；Ni也是保持钢中低温韧性的主要元素。因此，本发明中Ni含量控制在9.00％～11.00％。
Ni: Ni in the present invention is an austenite-forming element, which is crucial for expanding the austenite stable region, lowering the Ms point, and balancing with the Cr equivalent content to form the M+A dual-phase region falling within the Schaeffler equilibrium phase diagram. In addition, Ni also has the effects of solid solution strengthening and aging strengthening. It precipitates nano-scale Ni 3 Mo, Ni 3 Al, Ni 3 Ti and other strengthening phases with Mo, Al, and Ti during aging to achieve high strength; Ni is also the main element for maintaining low-temperature toughness in steel. Therefore, the Ni content in the present invention is controlled at 9.00% to 11.00%.
Mo：本发明充分利用Mo的强韧化作用和提高耐蚀性的作用。Mo能降低Ms点、扩大奥氏体稳定区，有利于在马氏体时效不锈钢中获得一定含量的残余奥氏体，确保钢的低温韧性。Mo也可在马氏体时效不锈钢中起到固溶强化作用，并与Ni作用时效析出纳米级Ni
3Mo强化相，发挥其显著的强化作用。此外，在马氏体时效不锈钢中合金元素Mo还可以阻止析出相沿原奥氏体晶界析出，从而避免沿晶断裂、提高断裂韧性。本发明中Mo含量控制在2.0％～4.0％范围内。
Mo: The present invention makes full use of the toughening and corrosion resistance-enhancing effects of Mo. Mo can lower the Ms point and expand the austenite stable zone, which is beneficial to obtain a certain amount of residual austenite in maraging stainless steel and ensure the low-temperature toughness of the steel. Mo can also play a role in solid solution strengthening in maraging stainless steel, and react with Ni to precipitate nano-scale Ni 3 Mo strengthening phases through aging, exerting its significant strengthening effect. In addition, the alloying element Mo in maraging stainless steel can also prevent the precipitation phase from precipitating along the original austenite grain boundaries, thereby avoiding intergranular fracture and improving fracture toughness. In the present invention, the Mo content is controlled within the range of 2.0% to 4.0%.
Ti：在马氏体时效不锈钢中Ti是最有效的时效强化合金元素之一，Ti与Ni时效析出纳米级的Ni
3Ti强化相，可以大幅度提高钢的强度。但是，Ti对马氏体时效不锈钢的韧性却存在削弱甚至危害作用，虽然添加少量的Ti即可显著增加钢的强度，但韧性却会显著下降。Ti对强韧性的显著影响已在同类马氏体时效不锈钢S03中得到验证。由于Ti在钢中属于易偏析元素，少量的偏析即可对强度和韧性造成显著的影响，如在S03钢中，当Ti含量从0.20％提高到0.25％，即可使-196℃的低温韧性从80J以上急剧降低到30J以下，导致性能不合格。对于大型铸锻件而言，宏观偏析很难避免或消除，如果利用Ti强化则极易导致大锻件性能不合格，且其对应的热处理工艺窗口十分狭窄，给工程化应用造成极 大的困难，甚至不能实现工程化应用。此外，Ti易与马氏体时效不锈钢中有害元素C、S、N结合，形成TiN、TiCN、TiCS等夹杂物，由于大型铸锻件凝固时间长，这些夹杂物的析出温度又很高，这些夹杂物将充分长大甚至达到几十个微米级，在锻造或轧制过程中很难破碎或细化，严重危害马氏体时效不锈钢的低温冲击韧性和疲劳性能。因此，本发明舍弃了Ti的强化作用而充分利用Mo的强韧化作用，由于马氏体时效不锈钢中C含量一般控制在100ppm量级以内，晶间腐蚀问题亦基本消除。因此，本发明将Ti含量控制在0.05％以下即可。
Ti: Ti is one of the most effective ageing strengthening alloying elements in martensitic aging stainless steel. Ti and Ni age and precipitate nano-scale Ni 3 Ti strengthening phases, which can greatly improve the strength of steel. However, Ti weakens or even harms the toughness of martensitic aging stainless steel. Although adding a small amount of Ti can significantly increase the strength of steel, the toughness will decrease significantly. The significant effect of Ti on strength and toughness has been verified in the similar martensitic aging stainless steel S03. Since Ti is an element that is easy to segregate in steel, a small amount of segregation can have a significant impact on strength and toughness. For example, in S03 steel, when the Ti content increases from 0.20% to 0.25%, the low-temperature toughness at -196℃ can be sharply reduced from more than 80J to less than 30J, resulting in unqualified performance. For large castings and forgings, macro segregation is difficult to avoid or eliminate. If Ti is used for strengthening, it is very easy to cause unqualified performance of large forgings, and the corresponding heat treatment process window is very narrow, which causes great difficulties for engineering applications, and even cannot achieve engineering applications. In addition, Ti is easy to combine with harmful elements C, S, and N in maraging stainless steel to form inclusions such as TiN, TiCN, and TiCS. Since the solidification time of large castings and forgings is long, the precipitation temperature of these inclusions is very high. These inclusions will grow fully and even reach dozens of micrometers. It is difficult to break or refine them during forging or rolling, which seriously harms the low-temperature impact toughness and fatigue performance of maraging stainless steel. Therefore, the present invention abandons the strengthening effect of Ti and makes full use of the strengthening and toughening effect of Mo. Since the C content in maraging stainless steel is generally controlled within the order of 100ppm, the intergranular corrosion problem is also basically eliminated. Therefore, the present invention controls the Ti content to be below 0.05%.
Al：通常作为钢中脱氧剂加入，为保证本发明中钢充分脱氧，将Al含量控制在0.080％以内。Al: usually added as a deoxidizer in steel. To ensure that the steel in the present invention is fully deoxidized, the Al content is controlled within 0.080%.
本发明所述马氏体时效不锈钢为超低温工程用钢，为保证-196℃下的高强低温韧性，钢中有害元素必须严格控制，本发明要求钢中有害元素按如下范围控制，且在综合考虑生产成本的情况下越低越好：P≤0.010％，S≤0.008％，[O]≤0.005％，[N]≤0.010％，[H]≤3ppm，As、Sn、Sb分别控制在0.005％以下，Cu≤0.20％，Ca≤0.05％。The maraging stainless steel of the present invention is ultra-low temperature engineering steel. In order to ensure high strength and low temperature toughness at -196°C, harmful elements in the steel must be strictly controlled. The present invention requires that the harmful elements in the steel be controlled within the following ranges, and the lower the better in consideration of production costs: P≤0.010%, S≤0.008%, [O]≤0.005%, [N]≤0.010%, [H]≤3ppm, As, Sn, Sb are controlled below 0.005% respectively, Cu≤0.20%, Ca≤0.05%.
以下实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。下述实施例中所用方法如无特别说明均为常规方法。The following examples are implemented on the premise of the technical solution of the present invention, and provide detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to the following examples. The methods used in the following examples are conventional methods unless otherwise specified.
【实施例1】[Example 1]
本实施例中，高强高韧马氏体时效不锈钢钢锭采用50kg真空感应炉冶炼，成分如表1所示。合金成分设计以Mo作为主要强化元素，Mo含量提高到2.52％；舍弃了Ti的强化作用，Ti含量降低到0.01％以下；Al含量作为脱氧剂加入，控制在0.05％。其他有害元素C、Si、Mn、P、S均控制在较低水平。In this embodiment, a high-strength and high-toughness martensitic aged stainless steel ingot is smelted in a 50kg vacuum induction furnace, and the composition is shown in Table 1. The alloy composition is designed with Mo as the main strengthening element, and the Mo content is increased to 2.52%; the strengthening effect of Ti is abandoned, and the Ti content is reduced to less than 0.01%; the Al content is added as a deoxidizer and controlled at 0.05%. Other harmful elements C, Si, Mn, P, and S are all controlled at a low level.
钢锭经过1200℃×24h高温均质化扩散退火，锻造成截面尺寸为80mm×80mm的方形坯料，再加工成性能试样坯料，然后经固溶处理和时效处理后加工成性能试样和金相试样。The steel ingot is subjected to high temperature homogenization diffusion annealing at 1200℃×24h, forged into a square billet with a cross-sectional size of 80mm×80mm, and then processed into a performance sample billet, and then processed into performance samples and metallographic samples after solution treatment and aging treatment.
本实施例中，力学性能检测按照GB/T228《金属材料室温拉伸试验方法》、GB/T229《金属材料夏比摆锤冲击试验方法》的要求进行。疲劳性能按GB T 4337-2015《金属材料疲劳试验旋转弯曲方法》测试圆柱形旋转弯曲疲劳性能，在PQ1-6型纯弯曲疲劳试验机上进行实验。In this embodiment, the mechanical property test is carried out in accordance with the requirements of GB/T228 "Metallic Materials Room Temperature Tensile Test Method" and GB/T229 "Metallic Materials Charpy Pendulum Impact Test Method". The fatigue performance is tested according to GB T 4337-2015 "Metallic Materials Fatigue Test Rotational Bending Method" to test the cylindrical rotational bending fatigue performance, and the experiment is carried out on a PQ1-6 pure bending fatigue testing machine.
本实施例中钢的力学性能检测结果如表2所示。经过两种热处理，即750℃×2h+500℃×2h和850℃×2h+700℃×2h+750℃×2h+500℃×2h后，室温抗拉强度Rm和屈服强度 R0.2分别大于1000MPa和950MPa，室温冲击韧性大于160J，-196℃冲击韧性大于100J。常温疲劳强度σ
-1大于565MPa，疲劳S-N曲线如图1所示。
The mechanical properties test results of the steel in this embodiment are shown in Table 2. After two heat treatments, namely 750℃×2h+500℃×2h and 850℃×2h+700℃×2h+750℃×2h+500℃×2h, the room temperature tensile strength Rm and yield strength R0.2 are greater than 1000MPa and 950MPa respectively, the room temperature impact toughness is greater than 160J, and the -196℃ impact toughness is greater than 100J. The room temperature fatigue strength σ -1 is greater than 565MPa, and the fatigue SN curve is shown in Figure 1.
本发明所述高强高韧马氏体时效不锈钢能在宽广的热处理工艺范围获得良好的强韧性和低温韧性，表2中实施例1的热处理工艺只是其中的典型代表。The high-strength and high-toughness martensitic aged stainless steel of the present invention can obtain good strength and low-temperature toughness in a wide range of heat treatment processes, and the heat treatment process of Example 1 in Table 2 is only a typical representative thereof.
【实施例2】[Example 2]
本实施例中，高强高韧马氏体时效不锈钢钢锭采用50kg真空感应炉冶炼，成分如表1中实施例2所示。合金成分设计以Mo作为主要强化元素，Mo含量提高到3.90％；舍弃了Ti的强化作用，Ti含量降低到0.04％；Al含量作为脱氧剂加入，控制在0.07％。其他有害元素C、Si、Mn、P、S均控制在较低水平。In this embodiment, a high-strength and high-toughness martensitic aged stainless steel ingot is smelted in a 50kg vacuum induction furnace, and the composition is shown in Example 2 in Table 1. The alloy composition is designed with Mo as the main strengthening element, and the Mo content is increased to 3.90%; the strengthening effect of Ti is abandoned, and the Ti content is reduced to 0.04%; the Al content is added as a deoxidizer and controlled at 0.07%. Other harmful elements C, Si, Mn, P, and S are all controlled at a low level.
钢锭经过1200℃×24h高温均质化扩散退火，锻造成截面尺寸为80mm×80mm的方形坯料，再加工成性能试样坯料，然后经固溶处理和时效处理后加工成性能试样和金相试样。The steel ingot is subjected to high temperature homogenization diffusion annealing at 1200℃×24h, forged into a square billet with a cross-sectional size of 80mm×80mm, and then processed into a performance sample billet, and then processed into performance samples and metallographic samples after solution treatment and aging treatment.
本实施例中，力学性能检测按照GB/T228《金属材料室温拉伸试验方法》、GB/T229《金属材料夏比摆锤冲击试验方法》的要求进行。疲劳性能按GB T 4337-2015《金属材料疲劳试验旋转弯曲方法》测试圆柱形旋转弯曲疲劳性能，在PQ1-6型纯弯曲疲劳试验机上进行实验。In this embodiment, the mechanical property test is carried out in accordance with the requirements of GB/T228 "Metallic Materials Room Temperature Tensile Test Method" and GB/T229 "Metallic Materials Charpy Pendulum Impact Test Method". The fatigue performance is tested according to GB T 4337-2015 "Metallic Materials Fatigue Test Rotational Bending Method" to test the cylindrical rotational bending fatigue performance, and the experiment is carried out on a PQ1-6 pure bending fatigue testing machine.
本实施例中钢的力学性能检测结果如表2所示。经过两种热处理，即750℃×2h+500℃×2h和850℃×2h+700℃×2h+750℃×2h+500℃×2h后，室温抗拉强度Rm和屈服强度R0.2分别大于1150MPa和1080MPa，室温冲击韧性大于150J，-196℃冲击韧性大于90J，常温疲劳强度σ
-1大于580MPa。
The mechanical property test results of the steel in this embodiment are shown in Table 2. After two heat treatments, namely 750℃×2h+500℃×2h and 850℃×2h+700℃×2h+750℃×2h+500℃×2h, the room temperature tensile strength Rm and yield strength R0.2 are greater than 1150MPa and 1080MPa respectively, the room temperature impact toughness is greater than 150J, the -196℃ impact toughness is greater than 90J, and the room temperature fatigue strength σ -1 is greater than 580MPa.
本发明所述高强高韧马氏体时效不锈钢能在宽广的热处理工艺范围获得良好的强韧性和低温韧性，表2中实施例2的热处理工艺只是其中的典型代表。The high-strength and high-toughness martensitic aged stainless steel of the present invention can obtain good strength and low-temperature toughness in a wide range of heat treatment processes, and the heat treatment process of Example 2 in Table 2 is only a typical representative thereof.
【实施例3】[Example 3]
本实施例中，高强高韧马氏体时效不锈钢钢锭采用50kg真空感应炉冶炼，成分如表1所示。合金成分设计以Mo作为主要强化元素，Mo含量提高到2.10％；舍弃了Ti的强化作用，Ti残留含量降低到0.002％；Al含量作为脱氧剂加入，控制在0.015％。其他有害元素C、Si、Mn、P、S均控制在较低水平。In this embodiment, a high-strength and high-toughness martensitic aged stainless steel ingot is smelted in a 50kg vacuum induction furnace, and the composition is shown in Table 1. The alloy composition is designed with Mo as the main strengthening element, and the Mo content is increased to 2.10%; the strengthening effect of Ti is abandoned, and the residual Ti content is reduced to 0.002%; the Al content is added as a deoxidizer and controlled at 0.015%. Other harmful elements C, Si, Mn, P, and S are all controlled at a low level.
钢锭经过1200℃×24h高温均质化扩散退火，锻造成截面尺寸为80mm×80mm的方形 坯料，再加工成性能试样坯料，然后经固溶处理和时效处理后加工成性能试样和金相试样。The steel ingot is subjected to high temperature homogenization diffusion annealing at 1200℃×24h, forged into a square billet with a cross-sectional size of 80mm×80mm, and then processed into a performance sample billet, and then processed into performance samples and metallographic samples after solution treatment and aging treatment.
本实施例中，力学性能检测按照GB/T228《金属材料室温拉伸试验方法》、GB/T229《金属材料夏比摆锤冲击试验方法》的要求进行。疲劳性能按GB T 4337-2015《金属材料疲劳试验旋转弯曲方法》测试圆柱形旋转弯曲疲劳性能，在PQ1-6型纯弯曲疲劳试验机上进行实验。In this embodiment, the mechanical property test is carried out in accordance with the requirements of GB/T228 "Metallic Materials Room Temperature Tensile Test Method" and GB/T229 "Metallic Materials Charpy Pendulum Impact Test Method". The fatigue performance is tested according to GB T 4337-2015 "Metallic Materials Fatigue Test Rotational Bending Method" to test the cylindrical rotational bending fatigue performance, and the experiment is carried out on a PQ1-6 pure bending fatigue testing machine.
本实施例中钢的力学性能检测结果如表2所示。经过两种热处理，即750℃×2h+500℃×2h和850℃×2h+700℃×2h+750℃×2h+500℃×2h后，室温抗拉强度Rm和屈服强度R0.2分别大于950MPa和905MPa，室温冲击韧性大于175J，-196℃冲击韧性大于120J，常温疲劳强度σ
-1大于540MPa。
The mechanical property test results of the steel in this embodiment are shown in Table 2. After two heat treatments, namely 750℃×2h+500℃×2h and 850℃×2h+700℃×2h+750℃×2h+500℃×2h, the room temperature tensile strength Rm and yield strength R0.2 are greater than 950MPa and 905MPa respectively, the room temperature impact toughness is greater than 175J, the -196℃ impact toughness is greater than 120J, and the room temperature fatigue strength σ -1 is greater than 540MPa.
本发明所述高强高韧马氏体时效不锈钢能在宽广的热处理工艺范围获得良好的强韧性和低温韧性，表2中实施例3的热处理工艺只是其中的典型代表。The high-strength and high-toughness martensitic aged stainless steel of the present invention can obtain good strength and low-temperature toughness in a wide range of heat treatment processes, and the heat treatment process of Example 3 in Table 2 is only a typical representative thereof.
【对比例1】[Comparative Example 1]
本对比例采用50kg真空感应炉冶炼马氏体时效不锈钢S03钢，成分如表1所示。对比例1中合金成分Cr、Ni、Mo均按S03钢的上限范围控制，与实施例1相比，Mo含量降低到0.71％，Ti含量增加到0.16％，即主要以Ti作为强化元素，Al作为脱氧剂其含量控制在0.02％，其他有害元素C、Si、Mn、P、S均控制在较低水平。This comparative example adopts a 50kg vacuum induction furnace to smelt martensitic aging stainless steel S03 steel, and the composition is shown in Table 1. In comparative example 1, the alloy components Cr, Ni, and Mo are all controlled according to the upper limit range of S03 steel. Compared with Example 1, the Mo content is reduced to 0.71%, and the Ti content is increased to 0.16%, that is, Ti is mainly used as a strengthening element, and Al is used as a deoxidizer, and its content is controlled at 0.02%, and other harmful elements C, Si, Mn, P, and S are all controlled at a relatively low level.
钢锭经过1200℃×24h高温均质化扩散退火，锻造成截面尺寸为80mm×80mm方形坯料，加工成性能试样坯料，然后经固溶处理和时效处理后加工成性能试样和金相试样。The steel ingot is subjected to high temperature homogenization diffusion annealing at 1200℃×24h, forged into a square billet with a cross-sectional size of 80mm×80mm, processed into a performance sample billet, and then processed into performance samples and metallographic samples after solution treatment and aging treatment.
本对比例中S03钢的力学性能检测结果如表2所示。The mechanical properties test results of S03 steel in this comparative example are shown in Table 2.
本对比例中，经过优化的两种热处理工艺，即750℃×2h+500℃×2h和850℃×2h+700℃×2h+750℃×2h+500℃×2h后，S03钢的室温抗拉强度Rm和屈服强度R
0.2分别比实施例1略高，达到了1000MPa以上，但其屈强比很高的同时塑性变差，室温冲击韧性比实施例1略好，达到170J以上，但是在-196℃温度下冲击韧性明显恶化且极不稳定，采用第一种热处理方式的冲击功仅为46J，采用第二种热处理方式的冲击功与实施例1持平，而采用其他热处理工艺亦很难改变这一现象。
In this comparative example, after two optimized heat treatment processes, namely 750℃×2h+500℃×2h and 850℃×2h+700℃×2h+750℃×2h+500℃×2h, the room temperature tensile strength Rm and yield strength R0.2 of S03 steel are slightly higher than those in Example 1, reaching more than 1000MPa, but its yield strength ratio is very high and its plasticity is poor. The room temperature impact toughness is slightly better than that in Example 1, reaching more than 170J, but the impact toughness is significantly deteriorated and extremely unstable at -196℃. The impact energy of the first heat treatment method is only 46J, and the impact energy of the second heat treatment method is the same as that of Example 1. It is also difficult to change this phenomenon by using other heat treatment processes.
本对比例中，选取强韧性最佳配合的试样测定的常温疲劳强度达到505MPa，疲劳S-N曲线如图2所示，常温疲劳强度与实施例1相比明显降低(低了60MPa)。另外，本对比例的热处理工艺窗口相对与实施例1明显变窄，对工程化热处理造成一定困难。In this comparative example, the room temperature fatigue strength of the sample with the best strength and toughness combination reached 505 MPa, and the fatigue S-N curve is shown in Figure 2. The room temperature fatigue strength is significantly lower (60 MPa lower) than that of Example 1. In addition, the heat treatment process window of this comparative example is significantly narrower than that of Example 1, which causes certain difficulties for engineering heat treatment.
【对比例2】[Comparative Example 2]
本对比例采用50kg真空感应炉冶炼马氏体时效不锈钢S03钢，成分如表1所示。本对比例中合金成分Cr、Ni、Mo均按S03钢的上限范围控制，与实施例1相比，Mo含量降低到0.71％，以Ti作为主强化元素进一步增加其含量，达到控制范围的上限0.25％，Al作为脱氧剂其含量控制在0.06％，其他有害元素C、Si、Mn、P、S均控制在较低水平。In this comparative example, a 50kg vacuum induction furnace is used to smelt martensitic aging stainless steel S03 steel, and the composition is shown in Table 1. In this comparative example, the alloy components Cr, Ni, and Mo are all controlled according to the upper limit range of S03 steel. Compared with Example 1, the Mo content is reduced to 0.71%, and Ti is used as the main strengthening element to further increase its content to reach the upper limit of the control range of 0.25%. Al is used as a deoxidizer and its content is controlled at 0.06%, and other harmful elements C, Si, Mn, P, and S are all controlled at a relatively low level.
钢锭经过1200℃×24h高温均质化扩散退火，锻造成截面尺寸为80mm×80mm方形坯料，加工成性能试样坯料，然后经固溶处理和时效处理后，加工成性能试样和金相试样。The steel ingot is subjected to high temperature homogenization diffusion annealing at 1200℃×24h, forged into a square billet with a cross-sectional size of 80mm×80mm, processed into a performance sample billet, and then processed into performance samples and metallographic samples after solution treatment and aging treatment.
本对比例中S03钢的力学性能检测结果如表2所示。The mechanical properties test results of S03 steel in this comparative example are shown in Table 2.
本对比例中，经过最佳的两种热处理工艺，即750℃×2h+500℃×2h和850℃×2h+600℃×2h+750℃×2h+500℃×2h后，S03钢的室温抗拉强度Rm和屈服强度R
0.2波动很大，波动范围在900～1100MPa，塑性很低，室温冲击韧性低于实施例1和对比例1。在-196℃温度下冲击韧性显著变差，最高仅37J，采用其它热处理工艺亦无法提升其低温韧性。
In this comparative example, after the two best heat treatment processes, i.e., 750℃×2h+500℃×2h and 850℃×2h+600℃×2h+750℃×2h+500℃×2h, the room temperature tensile strength Rm and yield strength R 0.2 of S03 steel fluctuate greatly, ranging from 900 to 1100MPa, the plasticity is very low, and the room temperature impact toughness is lower than that of Example 1 and Comparative Example 1. The impact toughness deteriorates significantly at -196℃, with a maximum of only 37J, and other heat treatment processes cannot improve its low temperature toughness.
表1实施例与对比例的马氏体时效不锈钢成分(重量百分比wt.％)Table 1 Maraging stainless steel composition of the embodiment and the comparative example (weight percentage wt.%)
表2实施例与对比例的马氏体时效不锈钢的力学性能(拉伸、疲劳性能为室温测试)Table 2 Mechanical properties of maraging stainless steel of the embodiment and comparative example (tensile and fatigue properties are tested at room temperature)
通过以上实施例及对比例表明，本发明所述一种超低温工程用高强高韧马氏体时效不锈钢与常规的S03钢相比，无论是在常温还是低温下，均具有良好稳定的强韧化匹配，疲劳性能明显优于S03钢，且热处理工艺窗口宽广，特别适合于生产大型装备所需的大型铸锻件，在航空航天、海洋工程、能源工程等方面均具有广泛的应用前景。The above embodiments and comparative examples show that the ultra-low temperature engineering high-strength and high-toughness martensitic aging stainless steel of the present invention has good and stable strength-toughness matching compared with conventional S03 steel, both at room temperature and low temperature, and its fatigue performance is significantly better than that of S03 steel, and its heat treatment process window is wide, so it is particularly suitable for the production of large castings and forgings required for large equipment, and has broad application prospects in aerospace, marine engineering, energy engineering and the like.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.
Claims (8)
- 一种超低温工程用高强高韧马氏体时效不锈钢，其特征在于，按重量百分比计，其成分包括：Cr 11.00％～13.00％，Ni 9.00％～11.00％，Mo 2.00％～4.00％，Ti≤0.05％，Al 0.001％～0.080％；钢中有害元素C≤0.03％，Si≤0.10％，Mn≤0.10％，P≤0.010％，S≤0.008％，[O]≤0.005％，[N]≤0.010％，[H]≤3ppm，Ca≤0.05％，Cu≤0.20％，As≤0.005％，Sn≤0.005％，Sb≤0.005％；余量为铁和不可避免的杂质。A high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering, characterized in that, in terms of weight percentage, its components include: Cr 11.00% to 13.00%, Ni 9.00% to 11.00%, Mo 2.00% to 4.00%, Ti≤0.05%, Al 0.001% to 0.080%; harmful elements C≤0.03%, Si≤0.10%, Mn≤0.10%, P≤0.010%, S≤0.008%, [O]≤0.005%, [N]≤0.010%, [H]≤3ppm, Ca≤0.05%, Cu≤0.20%, As≤0.005%, Sn≤0.005%, Sb≤0.005%; the remainder is iron and unavoidable impurities.
- 如权利要求1所述一种超低温工程用高强高韧马氏体时效不锈钢的制造方法，其特征在于，包括如下步骤：The method for manufacturing high-strength and high-toughness martensitic aging stainless steel for ultra-low temperature engineering as claimed in claim 1 is characterized by comprising the following steps:1)制备钢锭或铸锻件坯料；1) Prepare steel ingots or casting and forging blanks;2)热加工：钢锭或锻件坯料于1200℃±15℃均匀化处理24小时以上，锻造或轧制成板材或初始坯料，始锻温度或开轧温度为1100～1200℃；2) Hot working: The steel ingot or forging blank is homogenized at 1200℃±15℃ for more than 24 hours, forged or rolled into a plate or initial blank, and the initial forging temperature or rolling temperature is 1100～1200℃;3)一次固溶处理：600～800℃保温2～14小时，冷却至室温；3) Primary solution treatment: 600-800℃ for 2-14 hours, then cool to room temperature;4)时效处理：450～550℃保温2～20小时，空冷至室温。4) Aging treatment: keep at 450-550℃ for 2-20 hours, and air cool to room temperature.
- 根据权利要求2所述的一种超低温工程用高强高韧马氏体时效不锈钢的制造方法，其特征在于，所述步骤1)中，钢锭或铸锻件坯料采用超低碳超纯铁或高纯合金原料，经真空感应制取电极棒，然后经电渣重熔+真空自耗冶炼获得。The method for manufacturing high-strength and high-toughness martensitic aged stainless steel for ultra-low temperature engineering according to claim 2 is characterized in that in the step 1), the steel ingot or casting and forging blank is made of ultra-low carbon ultra-pure iron or high-purity alloy raw material, the electrode rod is prepared by vacuum induction, and then obtained by electroslag remelting + vacuum consumable smelting.
- 根据权利要求2所述的一种超低温工程用高强高韧马氏体时效不锈钢的制造方法，其特征在于，所述步骤1)中，钢锭或铸锻件坯料采用超低碳超纯铁或高纯合金原料，经AOD或VOD精炼，采用模铸或连铸制取电极棒，然后经电渣重熔+真空自耗冶炼获得。The method for manufacturing high-strength and high-toughness martensitic aged stainless steel for ultra-low temperature engineering according to claim 2 is characterized in that in the step 1), the steel ingot or casting and forging blank is made of ultra-low carbon ultra-pure iron or high-purity alloy raw material, refined by AOD or VOD, and the electrode rod is made by die casting or continuous casting, and then obtained by electroslag remelting + vacuum consumable smelting.
- 根据权利要求3或4所述的一种超低温工程用高强高韧马氏体时效不锈钢的制造方法，其特征在于，所述钢锭或铸锻件坯料的重量大于20吨时，制取电极棒后经真空自耗+电渣重熔获得，或制取电极棒后经电渣重熔+真空自耗+真空同质复合制坯获得。The method for manufacturing a high-strength and high-toughness martensitic aged stainless steel for ultra-low temperature engineering according to claim 3 or 4 is characterized in that when the weight of the steel ingot or casting and forging blank is greater than 20 tons, the electrode rod is prepared and then subjected to vacuum consumable + electroslag remelting, or the electrode rod is prepared and then subjected to electroslag remelting + vacuum consumable + vacuum homogeneous composite billet making to obtain it.
- 根据权利要求2所述的一种超低温工程用高强高韧马氏体时效不锈钢的制造方法，其特征在于，所述步骤2)中，钢锭的轧制比不小于3，锻件坯料的锻造比不小于3。The method for manufacturing high-strength and high-toughness martensitic aged stainless steel for ultra-low temperature engineering according to claim 2 is characterized in that, in the step 2), the rolling ratio of the steel ingot is not less than 3, and the forging ratio of the forging blank is not less than 3.
- 根据权利要求2所述的一种超低温工程用高强高韧马氏体时效不锈钢的制造方法，其特征在于，所述步骤3)中，冷却采用水冷、油冷或空冷。The method for manufacturing high-strength and high-toughness martensitic aged stainless steel for ultra-low temperature engineering according to claim 2 is characterized in that in the step 3), cooling is carried out by water cooling, oil cooling or air cooling.
- 根据权利要求2所述的一种超低温工程用高强高韧马氏体时效不锈钢的制造方法，其特征在于，所制造的钢板力学性能为：Rm≥950MPa，Re≥900MPa，A≥15％，Z≥60％， HV≥300，纵向Kv2≥150J，横向Kv2≥100J，疲劳强度σ -1≥500MPa；-196℃的冲击韧性为：纵向Kv2≥80J，横向Kv2≥55J。 The method for manufacturing a high-strength and high-toughness martensitic aged stainless steel for ultra-low temperature engineering according to claim 2 is characterized in that the mechanical properties of the manufactured steel plate are: Rm≥950MPa, Re≥900MPa, A≥15%, Z≥60%, HV≥300, longitudinal Kv2≥150J, transverse Kv2≥100J, fatigue strength σ -1 ≥500MPa; the impact toughness at -196°C is: longitudinal Kv2≥80J, transverse Kv2≥55J.
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| WO (1) | WO2024082324A1 (en) |
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| CN115595504A (en) | 2023-01-13 |
| CN115595504B (en) | 2024-01-12 |
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