CN108165891B - Extreme environment-resistant high-strength high-toughness low-carbon martensitic cast steel and preparation method thereof - Google Patents
Extreme environment-resistant high-strength high-toughness low-carbon martensitic cast steel and preparation method thereof Download PDFInfo
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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
- 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
- C21D1/18—Hardening; Quenching with or without subsequent 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
- C21D6/04—Hardening by cooling below 0 degrees Celsius
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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
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
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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
- 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
- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
Abstract
An extreme environment resistant high-strength high-toughness low-carbon martensite cast steel and a preparation method thereof, belonging to the technical field of low-carbon alloy cast steel heat treatment process. The invention carries out different proportions by using relatively simple and easily obtained raw materials, and adopts vacuum melting for casting. The high-strength high-toughness low-carbon martensite cast steel material is obtained through a series of heat treatment processes. The cast steel has the advantages of excellent comprehensive mechanical property, excellent combination of strength and toughness, particularly higher low-temperature plasticity, higher strength and lower notch sensitivity under severe environmental conditions. The preparation method of the cast steel is simple to operate, energy-saving and environment-friendly, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of low-carbon alloy cast steel heat treatment processes, and particularly relates to extreme environment-resistant high-strength high-toughness low-carbon martensite cast steel and a preparation method thereof.
Background
The cast steel has excellent mechanical and physical and chemical properties, and is widely applied to the mechanical manufacturing industries of transportation, mines, petroleum, metallurgy, ships and the like. As a large steel casting producing country, only 2011, the whole-year steel casting yield of China reaches 1100 million tons, and the rise reaches 48%. Meanwhile, many key parts in the industrial sector are not suitable for roll forming due to shape and wall thickness, and cast steel materials for cast forming are used. Therefore, the cast steel industry has huge development potential and economic benefit. The harsh use environment (parts of the related weaponry, such as the impeller of certain weaponry is subjected to low temperature, heavy load, impact and the like during operation) puts higher requirements on the performance of cast steel: while ensuring high strength, cast steel is also required to have good low-temperature impact toughness and weldability. The traditional cast steel material has high carbon content, the strength and hardness of steel can be improved by the high carbon content, but the problems of poor plasticity and toughness, difficult welding and the like are caused inevitably, and the use requirement of the cast steel material cannot be met.
In view of the harsh requirements of the use environment on the low-temperature impact toughness and good weldability of cast steel, the design of cast steel is moving toward low carbon. The low-carbon design brings difficulty to the casting of the high-strength and high-toughness cast steel, but the progress of the casting technology provides a technical foundation and a development opportunity for the production of the cast steel. The low-carbon design inevitably causes the insufficiency of the strength and the hardness of the low-carbon cast steel, and in order to take the manufacturing cost factor of the cast steel into consideration, the total amount of alloy elements needs to be properly controlled, and the alloy elements cannot be added in a large amount. When the components of the low-carbon alloy cast steel are constant, the accurate control of the heat treatment process becomes a key factor for designing high-strength and high-toughness cast steel.
At present, castings applied to the cast steel market can be classified into three categories according to the structure: (1) ferrite plus pearlite type metallographic structures such as steels of ZG16Mn, ZG22Mn, 15MnTi, etc. are obtained mainly by normalizing or normalizing plus tempering. (2) Bainite steel is added with a small amount of pearlite type metallographic structure, mainly comprises 14MnMoVBRe and other steels, and the bainite cast steel is generally added with Mn, Mo, Cr and other alloy elements so as to ensure that the bainite structure can be obtained at a low cooling speed, has medium strength, good plastic initiating property and wear resistance, and is very wide in research and application. (3) The tempered martensite metallographic structure comprises Cr, Mn, Mo and Ni as main alloy elements. The cast steel can obtain higher comprehensive mechanical property mainly through rapid quenching or isothermal quenching treatment and proper tempering.
Disclosure of Invention
The invention aims to provide the high-strength high-toughness low-carbon martensitic cast steel resistant to the extreme environment and the preparation method thereof, and solves the problem that the cast steel still has excellent comprehensive mechanical properties under severe environmental conditions. Particularly, the high-toughness and high-plasticity steel plate comprises excellent toughness and toughness matching, good low-temperature plasticity, high strength and low notch sensitivity. The invention is realized by the following technical scheme:
the high-strength high-toughness low-carbon martensitic cast steel with extreme environment resistance comprises the following chemical components in percentage by mass: c: 0.01 to 0.2 percent of Cr: 10.0% -13.0%, Ni: 4.5% -6.5%, Mo: 3.0% -5.0%, Si: less than or equal to 0.5 percent, Mn: less than or equal to 0.5 percent, P: less than or equal to 0.01 percent, S: less than or equal to 0.01 percent, and the balance of iron and inevitable impurities.
The high-strength and high-toughness low-carbon martensitic cast steel has the room-temperature tensile strength of 1500-1600 MPa, the yield strength of 1200-1300 MPa, the elongation of 15-20%, the reduction of area of 40-60%, and the impact toughness aKU＞
50J/cm2，AKUGreater than 40J, low temperature (-70 ℃) impact toughness aKU＞40J/cm2，AKU＞33J。
A preparation method of extreme environment resistant high-strength high-toughness low-carbon martensite cast steel comprises the following specific steps and parameters:
1. the raw materials are taken according to the chemical component proportion of the cast steel calculated by mass percent, and the proportion is as follows: c: 0.01 to 0.2 percent of Cr: 10.0% -13.0%, Ni: 4.5% -6.5%, Mo: 3.0% -5.0%, Si: less than or equal to 0.5 percent, Mn: less than or equal to 0.5 percent, P: less than or equal to 0.01 percent, S: less than or equal to 0.01 percent, and the balance being iron.
Wherein Fe is one or more of pure iron, low-sulfur iron, ferrochrome, high-carbon ferrochrome, ferromolybdenum, ferrosilicon and ferromanganese;
wherein Cr is one or more of ferrochrome, metallic chromium, brocade ferrochrome, low-nitrogen brocade ferrochrome and high-purity low-oxygen chromium;
wherein Mo is one or more of metal molybdenum, ferromolybdenum and molybdenum chromium rods;
wherein Ni is one or more of electrolytic nickel, metallic nickel, gold nickel and high-purity nickel;
wherein Si is one or more of high-carbon silicon, high-carbon ferrosilicon, high-purity polysilicon and metal silicon particles;
wherein Mn is one or more of ferromanganese, metal manganese and electrolytic manganese sheets.
2. Fe, C, Cr and Ni are mixed and put into the bottom of the crucible, and Mo is proportionally loaded on the upper part of the crucible. Vacuumizing and heating within 15-30min to completely melt, controlling the temperature to 1600-1650 ℃, controlling the vacuum degree to be less than 0.1Pa, keeping for 10-30min, stopping heating, keeping for 5-15min, and adding Si, Mn and C; and (3) filling argon into the furnace to-0.02 to-0.1 MPa while adding the argon, and tapping and casting under the condition that the temperature is adjusted to be not lower than 1560 ℃.
3. Heating the cast to 1100-1200 ℃ from room temperature, preserving heat for 2-4 h, and cooling to room temperature for homogenization treatment. And then heating the mixture to 1050-1250 ℃ from the room temperature, preserving the heat for 1-3 h, and cooling the mixture to the room temperature. Freezing the casting at the temperature of minus 50 ℃ to minus 90 ℃ for 1 to 3 hours, air-cooling the casting to room temperature, and finally tempering the casting at the temperature of 450 ℃ to 550 ℃ for 2 to 4 hours to prepare the high-strength high-toughness low-carbon martensitic cast steel.
And cooling in the step 3 is air cooling, oil cooling, compressed air cooling or water cooling.
The invention has the advantages that:
1. the cast steel has excellent comprehensive mechanical properties, and compared with common cast steel, the cast steel has excellent toughness matching, tensile strength at room temperature can reach 1500-1600 MPa, yield strength is 1200-1300 MPa, elongation is 16-20%, and reduction of area is 40-60%, and the cast steel has the characteristics of excellent toughness matching, excellent plasticity, low notch sensitivity, small residual stress and the like;
2. good impact toughness at room temperature and low temperature, impact toughness aKU＞50J/cm2Impact energy AKUGreater than 40J, low temperature (-70 ℃) impact toughness aKU＞40J/cm2Impact work (-70 ℃ C.) AKUIs > 33J. The ductile-brittle transition temperature is lower than-70 ℃, and the product can be completely safely used in extreme environments.
3. The welding material has low carbon equivalent, small internal stress of the structure before and after welding, small tendency of welding crack and good welding performance. The cast steel contains certain amount of molybdenum, chromium and nickel elements, so that the cast steel has good corrosion resistance, wear resistance and high hardenability. The property that the cast steel has multiple purposes under extreme environments is increased.
4. The preparation method has the advantages of simple preparation process, low cost, low requirement on equipment, convenience in production and development, good energy-saving effect and higher production efficiency. After casting, forging or rolling is not needed, and the low-carbon martensite structure with excellent performance can be obtained only by simple quenching, freezing and tempering, so that a large amount of energy can be saved.
Drawings
FIG. 1 is a metallographic structure of a martensitic cast steel of the present invention before heat treatment.
FIG. 2 is a structural diagram of the martensitic cast steel of the present invention after heat treatment.
FIG. 3 is a scanning electron microscope image of a fracture of a sample of the martensitic cast steel of the present invention subjected to a Charpy impact test at-70 ℃.
FIG. 4 is a scanning electron microscope image of a fracture of a room temperature tensile test sample of the martensitic cast steel.
Detailed Description
Example 1
Mixing pure iron, chromium metal and nickel metal, placing the mixture into the bottom of a crucible, and dispersedly loading molybdenum metal on the middle upper part of the crucible. Vacuumizing and heating to be completely melted within 20min, controlling the temperature at 1600 ℃, controlling the vacuum degree at less than 0.1Pa, keeping the vacuum degree for 30min, stopping heating and keeping the vacuum degree for 15min, and adding high-carbon silicon and ferromanganese. While adding, argon gas is injected into the furnace to-0.02 MPa, and casting is carried out when the temperature is adjusted to 1560 ℃. The obtained cast steel comprises the following chemical components: 0.01%, Cr: 10.0%, Ni: 4.5%, Mo: 3.0%, Si: 0.2%, Mn: 0.3%, P: less than or equal to 0.01 percent, S: less than or equal to 0.01 percent, and the balance being iron. The metallographic structure of the cast steel obtained after casting is shown in fig. 1, and the alloy consists of ferrite, pearlite, a small amount of martensite and carbides. The matrix structure is ferrite, pearlite and a small amount of martensite, and is formed by transformation of primary austenite and eutectic austenite in the process of solidification and cooling. Heating the cast product obtained by casting from room temperature to 1100 ℃, preserving heat for 4h, and then cooling in air to room temperature for homogenization treatment. Then the temperature is raised to 1050 ℃ from room temperature, and the oil is cooled to room temperature after the temperature is preserved for 3 h. And (3) freezing the casting at-50 ℃ for 3h, air-cooling to room temperature, and finally tempering at 450 ℃ for 2h to prepare the high-strength high-toughness low-carbon martensitic cast steel. The structure of the cast steel is shown in fig. 2, and the alloy structure is a tempered lath martensite structure.
The structure of the obtained material is low-carbon tempered martensite, and the material has the characteristics of excellent combination of strength and toughness, excellent plasticity, low notch sensitivity, small residual stress and the like, and particularly has excellent low-temperature impact toughness. The fracture structure of the sample of the high-strength high-toughness low-carbon martensitic cast steel subjected to the Charpy impact test at-70 ℃ is shown in figure 3, and the fracture structure of the sample subjected to the room-temperature tensile test is shown in figure 4. It is evident from both figures that there are a large number of dimples in the fracture, indicating that both tensile and impact fractures are ductile. Tensile strength of 1520MPa, yield strength of 1230MPa, elongation of 20%, reduction of area of 60%, and impact toughness a at room temperatureKUIs 92J/cm2Impact energy AKU74J, low temperature (-70 ℃ C.) impact toughness aKUIs 53J/cm2Low temperature (-70 ℃) impact energy AKUWas 43J.
Example 2
Low-sulfur iron, bright iron chromium and electrolytic nickel are put into the bottom of the crucible, and ferromolybdenum is dispersedly arranged on the middle upper part of the crucible. Vacuumizing and heating to be completely melted within 20min, controlling the temperature at 1650 ℃, controlling the vacuum degree to be less than 0.1Pa, keeping the vacuum degree for 10min, stopping heating and keeping for 5min, and adding high-carbon ferrosilicon and manganese metal. While adding, argon gas was blown into the furnace to-0.1 MPa, and casting was carried out while adjusting the temperature at 1570 ℃. The obtained cast steel comprises the following chemical components: 0.2%, Cr: 13.0%, Ni: 6.5%, Mo: 5.0%, Si: 0.5%, Mn: 0.5%, P: less than or equal to 0.01 percent, S: less than or equal to 0.01 percent, and the balance being iron. Heating the cast product obtained by casting from room temperature to 1200 ℃, preserving heat for 2h, and cooling to room temperature by adopting compressed air. Then the temperature is increased from the room temperature to 1250 ℃, and the temperature is preserved for 1h and then the air is cooled to the room temperature. And (3) freezing the casting at the temperature of minus 90 ℃ for 1h, air-cooling the casting to room temperature, and finally tempering the casting at the temperature of 550 ℃ for 2h to prepare the high-strength high-toughness low-carbon martensitic cast steel.
The structure of the obtained material is low-carbon tempered martensite.The tensile strength at room temperature is 1600MPa, the yield strength is 1300MPa, the elongation is 16 percent, the reduction of area is 40 percent, and the impact toughness aKUIs 51J/cm2Impact energy AKU41J, low temperature (-70 ℃ C.) impact toughness aKUIs 41J/cm2Low temperature (-70 ℃) impact energy AKUIs 33J.
Example 3
High-carbon ferrochrome, ferrosilicon, ferromanganese, low-nitrogen brocade iron chromium and high-purity nickel are mixed and put at the bottom of the crucible, and molybdenum-chromium rods are dispersedly arranged at the middle upper part of the crucible. Vacuumizing and heating to be completely melted within 20min, controlling the temperature at 1630 ℃, controlling the vacuum degree to be less than 0.1Pa, keeping the vacuum degree for 20min, stopping heating and keeping the vacuum degree for 10min, and adding the metal silicon particles and the electrolytic manganese sheets. While adding, filling argon into the furnace to-0.05 MPa, and casting when adjusting the temperature to 1580 ℃. The obtained cast steel comprises the following chemical components: 0.16%, Cr: 12.0%, Ni: 5.5%, Mo: 4.2%, Si: 0.3%, Mn: 0.4%, P: less than or equal to 0.01 percent, S: less than or equal to 0.01 percent, and the balance being iron. Heating the cast product obtained by casting from room temperature to 1160 ℃, preserving heat for 3h, and cooling the cast product to room temperature by oil. Then the temperature is raised to 1100 ℃ from the room temperature, and the temperature is kept for 2h and then the water is cooled to the room temperature. And (3) freezing the casting at-80 ℃ for 2h, air-cooling to room temperature, and finally performing tempering at 490 ℃ for 3h to prepare the high-strength high-toughness low-carbon martensitic cast steel.
The structure of the obtained material is low-carbon tempered martensite. Tensile strength at room temperature of 1580MPa, yield strength of 1240MPa, elongation of 18%, reduction of area of 51%, impact toughness aKUIs 75J/cm2Impact energy AKU60.5J, low temperature (-70 ℃ C.) impact toughness aKUIs 47J/cm2Low temperature (-70 ℃) impact energy AKUIs 38J.
In conclusion, by reducing the carbon content and properly increasing the alloying elements of Cr, Ni and Mo, the contradiction between toughness matching, weldability and corrosion resistance existing when the tensile strength of cast steel is improved in the prior art is solved, and the problem of material performance reduction under extreme environments is solved. Thus providing the martensite cast steel which has simple operation, low cost and excellent casting comprehensive performance and is used for harsh environment. The high-impact high-strength high-impact-resistance casting is widely applied, not only can be applied to the casting which is used in an extreme environment and has large environmental change, high load and high impact, but also can be applied to impellers, hubs and turbines in other tanks, armored vehicles and large transport vehicles which have strict requirements on low-temperature environment and toughness matching, and can also be applied to high-standard railway wagon couplers, railway bridges, large structural frames, railway switches, wheels or hubs for high-precision high-speed railway trains and the like in a civil range.
Claims (2)
1. A preparation method of extreme environment resistant high-strength high-toughness low-carbon martensite cast steel is characterized by comprising the following specific steps and parameters:
1) the raw materials are taken according to the chemical component proportion of the cast steel calculated by mass percent, and the proportion is as follows: c: 0.01 to 0.2 percent of Cr: 10.0% -13.0%, Ni: 4.5% -6.5%, Mo: 3.0% -5.0%, Si: less than or equal to 0.5 percent, Mn: less than or equal to 0.5 percent, P: less than or equal to 0.01 percent, S: less than or equal to 0.01 percent, and the balance being iron;
wherein Fe is one or more of pure iron, low-sulfur iron, ferrochrome, ferromolybdenum, ferrosilicon and ferromanganese;
wherein Cr is one or two of ferrochrome and metal chromium;
wherein Mo is one or more of metal molybdenum, ferromolybdenum and molybdenum chromium rods;
wherein Ni is high-purity nickel;
wherein Si is one or more of high-carbon silicon, high-carbon ferrosilicon and high-purity polysilicon;
wherein Mn is one or two of ferromanganese and metal manganese sheets;
2) mixing Fe, C, Cr and Ni raw materials, putting the mixture into the bottom of a crucible, and proportionally filling Mo into the upper part of the crucible; vacuumizing and heating within 15-30min to completely melt, controlling the temperature to 1600-1650 ℃, controlling the vacuum degree to be less than 0.1Pa, keeping for 10-30min, stopping heating, keeping for 5-15min, and adding Si, Mn and C; adding argon into the furnace to-0.02-0.1 MPa while adding, adjusting the temperature, tapping and casting under the condition that the temperature is not lower than 1560 ℃;
3) heating the cast to 1100-1200 ℃ from room temperature, preserving heat for 2-4 h, and cooling to room temperature for homogenization treatment; then heating the mixture from room temperature to 1050-1250 ℃, preserving the heat for 1-3 h, and cooling the mixture to room temperature; freezing the casting at-50 to-90 ℃ for 1 to 3 hours, air-cooling to room temperature, and finally tempering at 450 to 550 ℃ for 2 to 4 hours to prepare the high-strength high-toughness low-carbon martensitic cast steel;
the high-strength high-toughness low-carbon martensitic cast steel resisting extreme environment comprises the following chemical components in percentage by mass: c: 0.01 to 0.2 percent of Cr: 10.0% -13.0%, Ni: 4.5% -6.5%, Mo: 3.0% -5.0%, Si: less than or equal to 0.5 percent, Mn: less than or equal to 0.5 percent, P: less than or equal to 0.01 percent, S: less than or equal to 0.01 percent, and the balance of iron and inevitable impurities;
the room-temperature tensile strength of the martensitic cast steel is 1500-1600 MPa, the yield strength is 1200-1300 MPa, the elongation is 15-20%, the reduction of area is 40-60%, and the impact toughness aKU＞50J/cm2，AKUMore than 40J, low temperature-70 ℃ impact toughness aKU＞40J/cm2，AKU＞33J。
2. The method of claim 1, wherein the cooling in step 3) is air cooling, oil cooling or water cooling.
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