CN113249654A - In-situ nanoparticle reinforced ultrahigh-strength steel for ocean engineering and preparation method thereof - Google Patents
In-situ nanoparticle reinforced ultrahigh-strength steel for ocean engineering and preparation method thereof Download PDFInfo
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Abstract
An in-situ nanoparticle reinforced ultrahigh-strength steel for ocean engineering and a preparation method thereof belong to the field of steel materials. Adding Ni and Co elements into the components, feeding Al- (1.5-30) wt.% Ti composite stranded wire into a steel melt containing O with the concentration of 5-100 PPm by a wire feeding and stirring method to obtain molten steel containing O, Al and Ti, wherein the molten steel contains precipitated phase Al which is higher than the melting point of a matrix alloy2O3And Ti3O5Along with the temperature reduction, the solubility of Al, Ti and O is reduced, and the large supercooling degree is formed at a fast cooling speed, and meanwhile, when the melt forms a large flowing linear velocity in the solidification process, Al2O3And Ti3O5Firstly, a large amount of in-situ nano-phase Al is obtained by precipitation2O3And Ti3O5And (4) ingot casting in a dispersion distribution mode. In-situ nanophase Al2O3And Ti3O5The steel can not only play a role in strengthening the second phase and improve the strength of the steel, but also can be used as a heterogeneous nucleation core to refine inclusions and reduce the grain size, thereby playing a role in strengthening fine grains. Finally, the yield strength of the high-strength steel is more than or equal to 1200MPa, and the elongation is more than or equal to 15%.
Description
Technical Field
The invention belongs to the field of steel materials, and relates to in-situ nanoparticle reinforced ultrahigh-strength steel for ocean engineering and a preparation method thereof.
Background
In recent years, with the increasing development of marine resources at home and abroad, higher and higher requirements are being made on the strength, low-temperature impact performance and the like of steel for marine engineering. The traditional preparation idea of the steel for ocean engineering mainly adopts high-carbon high-alloy and quenching and tempering treatment, and the technical route can basically meet the requirements of the steel for ocean engineering, but has the problems of poor weldability and the like. Meanwhile, the front heat and the back heat during welding also increase the process and the cost.
In order to solve the problems, high-toughness easy-welding nano Cu-rich phase strengthened HSLA steel is developed in the United states. The alloy is greatly reduced in carbon and carbon, and the Cu nanophase precipitated in the aging process is utilized to play a role in precipitation strengthening, so that the strength loss caused by the reduction of the carbon content is made up. The research status and trend of the weldability of the ultrahigh-strength hull structural steel, namely Leishangwei, Zhoushanbao, Huangdahua, the research report of materials, 2020, 34 (1) by Leishangwei et al are discovered through simulation analysis, and the introduction of Cu precipitation strengthening and the design of components for improving the Ni content can become the idea for further improving the weldability of the ultrahigh-strength hull structural steel. However, the Cu nanometer reinforced steel has the problems of poor thermal stability and the like, and the research of the Rooiman and the like [ Rooiman, Yancaifu, Suhang, Chaifeng, aging temperature influences the structure and the performance of the HSLA high-strength hull steel, and the material heat treatment bulletin, 2011, 32 (6) ] finds that the precipitation of Cu is obviously increased in an underaging state along with the increase of the aging temperature, the form of the Cu is changed from a spherical shape to a short rod shape or a rod shape, and the Cu and the matrix lose a coherent relationship. Therefore, the search for new methods for improving the strength of steel materials is an important direction for the development of high-strength steel.
Wangyantong et al [ Wangyantong, Tanghao, Chengxian, New construction ] A method for preparing in-situ nanoparticle reinforced Q195 steel: china, 201310409451.6.2016-04-27.] preparing Q195 steel by in-situ nanoparticle strengthening, adding Fe-Ti alloy wires during smelting and casting, applying pressure in a container to form a pressure field, and applying centrifugal force or electromagnetic stirring in the melt to form a nano-strengthened steel alloy. Through detecting that a large amount of nano second phases which are dispersed and distributed are precipitated in situ in the structure, compared with the original Q195 steel, the strength of the nano reinforced steel is greatly improved, and the plastic toughness of the nano reinforced steel is not greatly lost. Chen Hua et al [ Xiaohua Chen, Lili Qiu, Hao Tang, Xiang Luo, Longfei Zuo, Zidong Wang. Effect of nanoparticles for formed in liquid crystal microstructure and mechanical property of high strength h steel, Journal of Materials Processing Technology, 2015] studied in detail the difference in mechanical properties between A steel smelted in the conventional manner under the same composition and B steel fed with titanium wires to form in-situ nanophase during smelting, and found that the yield strength of B steel can reach 940MPa without much loss of ductility and toughness. Meanwhile, the in-situ nanophase plays a role in refining crystal grains and refining impurities as a heterogeneous nucleation core in the solidification process, and the performance of the steel is greatly improved. Wang Zidong et al [ Wang Zidong, Shirongjian, Pangxinlu, Qiaolijie, Chengxianghua, Wang Lei ] a high strength and toughness steel and its preparation method: china, 201810891265.3.2018-12-14, invents a high strength and toughness steel and a preparation method thereof, wherein the high strength and toughness steel comprises the following chemical components in percentage by weight: c: 0.01-0.1 wt.%, Si ≤ 0.15 wt.%, Mn: 1.0-2.0 wt.%, P.ltoreq.0.02 wt.%, S.ltoreq.0.005 wt.%, Ni: 4.0-5.0 wt.%, Cr: 0.2-1.0 wt.%, Mo: 0.4-1.0 wt.%, V: 0.02-0.08 wt.%, Nb: 0.02-0.10 wt.%, Al: 0.02-0.1 wt.%, Ti: 0.005-0.05 wt.%, and the balance Fe. Feeding fine alloy twisted wires in a melt in a regional micro-supply mode to form in-situ nano particles, and improving the strength of the steel without damaging the ductility and toughness of the steel. On the basis, Ni and Co elements are added, and an in-situ nanoparticle reinforced ultrahigh-strength steel for ocean engineering is invented by adopting an in-situ nanoparticle reinforcing mode, wherein the yield strength reaches 1200 MPa.
Disclosure of Invention
The invention aims to provide in-situ nano-particle reinforced ultrahigh-strength steel for ocean engineering and a preparation method thereof, on the basis of the high-strength and high-toughness steel invented in the patent CN 108998729A and the preparation method thereof, Ni and Co elements are added to form in-situ nano-particles in a melt, and the ultrahigh-strength steel with yield strength of more than or equal to 1200MPa and elongation of more than or equal to 15% is obtained through a rolling and heat treatment system matched with the in-situ nano-particles. The effect of adding Ni and Co elements is as follows: ni can improve the strength and plasticity of the steel plate and can also greatly improve the low-temperature impact toughness, because Ni only forms a solid solution in the steel, the solid solution strengthening effect is not obvious, the material plasticity is improved mainly by increasing a crystal lattice slip plane during plastic deformation, and Ni can also improve the hardenability of alloy steel, improve the toughness of the steel at low temperature and reduce the ductile-brittle transition temperature. Co can improve the strength of steel and is a strong solid solution strengthening element. The addition of Co can make Fe produce short-range order or long-range order, reduce self-diffusion coefficient of Fe, and delay the recovery of martensite dislocation substructure during tempering, so as to ensure the formation of fine and dispersed alloy carbide at dislocation.
The in-situ nano-particle reinforced ultrahigh-strength steel for ocean engineering comprises the following alloy chemical components in percentage by mass: c: 0.06-0.09%, Si: 0-0.1%, Mn: 0-0.15%, Ni: 9.0-11.0%, Cr: 1.5-2.0%, Mo: 0.8-1.0%, V: 0.03-0.04%, Ti: 0.006-0.010%, Al: 0.06-0.08%, Nb: 0.06-0.08%, Co: 7.0 to 8.0 percent.
The preparation method of the in-situ nanoparticle reinforced ultrahigh-strength steel for ocean engineering is characterized by firstly preparing a steel alloy melt containing nano precipitated phase elements, feeding Al- (1.5-30) wt.% Ti composite stranded wires with the diameter of 0.5-3 mm in a steel melt containing 5-100 PPm of O in a regional micro supply mode (i.e. a wire feeding and stirring method), and then solidifying at a fast cooling speed (more than 500K/min). Al above the melting point of the base alloy during solidification2O3And Ti3O5The precipitated phase is firstly precipitated, the nano crystal nucleus is rapidly carried away from the generated area by utilizing strong convection, the concentration gradient of the trace elements is destroyed, the dynamic and thermodynamic conditions required by growth cannot be achieved, the flow field, the concentration field and the force field of the melt are controlled, and a large amount of in-situ nano-phase Al which is dispersedly distributed is generated in the smelted material2O3And Ti3O5The steel has the advantages of strengthening the second phase, improving the strength of the steel, refining inclusions as heterogeneous nucleation cores, reducing the grain size and achieving the fine grain strengthening effect.
The preparation method of the in-situ nanoparticle reinforced ultrahigh-strength steel for ocean engineering is characterized by comprising the following specific process steps of:
(1) heating and melting the steel alloy by using a vacuum melting heating mode;
(2) after the steel is completely melted, overheating the steel by 50-100 ℃, measuring the oxygen content in the molten steel to be 5-100 PPm after the liquid level is stable, introducing argon into the furnace, and adding Al-Ti composite stranded wires with the diameter of 0.5-3 mm;
(3) under the protection of argon gas with the pressure of 0.01-0.5 MPa, alloy smelting is carried out, and pouring is carried out after Al-Ti composite stranded wires are melted and heat preservation is carried out for 1-5 min;
(4) pouring under the protection of argon at the pressure of 0.01-0.5 MPa, wherein the linear velocity of flowing of the molten metal in the pouring process is not lower than 1.7 m/s;
(5) controlling the cooling speed in the solidification process to be not lower than 500 ℃/min;
(6) obtaining a casting blank after the metal is completely solidified;
(7) subsequently, controlled rolling and controlled cooling are carried out, the total pass reduction is 70% -90% after multi-pass rolling, and the plate blank is placed into a furnace to be cooled to room temperature after final rolling to obtain a plate blank;
(8) performing water quenching and tempering, and then performing air cooling to obtain the steel plate; the yield strength of the steel is more than or equal to 1200MPa, and the elongation is more than or equal to 15%.
Further, the controlled rolling and controlled cooling process in the step (7) is that the temperature is kept at 1200-1250 ℃ for 2h, and the temperature ranges of initial rolling and final rolling are 1150-1200 ℃ and 850-900 ℃ respectively after multi-pass rolling.
Further, the water quenching temperature in the step (8) is as follows: 840 ℃ to 860 ℃, and the tempering temperature is 500 ℃ to 550 ℃.
The invention has the advantages that:
the elements of Ni and Co are added in the composition design, and a stable nano phase which is dispersed and distributed is generated in the steel melt, so that the second-phase strengthening and fine-grain strengthening effects are achieved, and the ultrahigh-strength steel with the yield strength of more than or equal to 1200MPa and the elongation of more than or equal to 15% is obtained.
Drawings
FIG. 1 is a photograph of a scanned tissue in an as-cast state;
FIG. 2 is a photograph of the transmission nanophase in the as-cast state.
Detailed Description
Other features, details and advantages of the present invention will become more fully apparent from the following detailed description of the specific embodiments of the invention when taken in conjunction with the accompanying drawings.
The invention is described in detail below by means of exemplary embodiments. It is pointed out that the person skilled in the art will readily understand that the following examples are given by way of illustration only and are not intended to limit the invention in any way.
Example 1:
(1) alloy chemical composition (mass percent): c: 0.09%, Si: 0.1%, Mn: 0.15%, Ni: 10.8%, Cr: 1.7%, Mo: 0.9%, V: 0.04%, Ti: 0.010%, Al: 0.06%, Nb: 0.07%, Co: 7.0 percent;
(2) heating and melting the steel alloy by using a vacuum melting and heating mode;
(3) the alloy smelting is carried out in an argon atmosphere;
(4) after the steel is completely melted, the steel is overheated to 50-100 ℃, after the liquid level is stable, Al-10 wt.% Ti composite stranded wire with the diameter of 2 mm is added after the oxygen content in the molten steel reaches 30 PPm, and the Al addition is 0.065 wt.% and the Ti addition is 0.007 wt.% through calculation;
(5) smelting under the protection of argon gas with the pressure of 0.5MPa, and pouring after Al-Ti composite stranded wires are melted and heat preservation is carried out for 3 min;
(6) pouring under the protection of argon gas with the pressure of 0.5MPa, wherein the linear velocity of flowing of the molten metal in the pouring process is not lower than 1.7 m/s;
(7) controlling the cooling speed in the solidification process to be not lower than 500 ℃/min;
(8) after the metal is completely solidified, obtaining a casting blank, sampling and carrying out structure analysis on the casting state, as shown in figure 1, and detecting that a large number of nano particles which are dispersedly distributed exist in the structure, as shown in figure 2;
(9) subsequently, controlled rolling and controlled cooling are carried out, heat preservation is carried out for 2 hours at 1250 ℃, 7 passes of rolling are carried out, the initial rolling temperature and the final rolling temperature are respectively 1200 ℃ and 900 ℃, the total rolling reduction rate is 82%, and the steel plate is placed into a furnace to be cooled to room temperature after the final rolling to obtain a plate blank;
(10) a heat treatment process: quenching at 860 deg.C for 30 min, and water quenching; tempering at 500 ℃, keeping the temperature for 120min, and air-cooling after tempering to obtain the steel plate;
(11) the room temperature tensile test was carried out on the sample to obtain the material mechanical properties shown in table 1.
TABLE 1
| Yield strength (MPa) | Tensile strength (MPa) | Elongation (%) |
| 1261 | 1366 | 15.4 |
Example 2:
(1) alloy chemical composition (mass percent): c: 0.09%, Si: 0.1%, Mn: 0.15%, Ni: 10.8%, Cr: 1.7%, Mo: 0.9%, V: 0.04%, Ti: 0.010%, Al: 0.06%, Nb: 0.07%, Co: 7.0 percent;
(2) heating and melting the steel alloy by using a vacuum melting and heating mode;
(3) the alloy smelting is carried out in an argon atmosphere;
(4) after the steel is completely melted, the steel is overheated to 50-100 ℃, after the liquid level is stable, Al-10 wt.% Ti composite stranded wire with the diameter of 2 mm is added after the oxygen content in the molten steel reaches 30 PPm, and the Al addition is 0.065 wt.% and the Ti addition is 0.007 wt.% through calculation;
(5) smelting under the protection of argon gas with the pressure of 0.5MPa, and pouring after Al-Ti composite stranded wires are melted and heat preservation is carried out for 3 min;
(6) pouring under the protection of argon gas with the pressure of 0.5MPa, wherein the linear velocity of flowing of the molten metal in the pouring process is not lower than 1.7 m/s;
(7) controlling the cooling speed in the solidification process to be not lower than 500 ℃/min;
(8) after the metal is completely solidified, obtaining a casting blank, sampling and carrying out structure analysis on the casting state, as shown in figure 1, and detecting that a large number of nano particles which are dispersedly distributed exist in the structure, as shown in figure 2;
(9) subsequently, controlled rolling and controlled cooling are carried out, heat preservation is carried out for 2 hours at 1250 ℃, 7 passes of rolling are carried out, the initial rolling temperature and the final rolling temperature are respectively 1200 ℃ and 900 ℃, the total rolling reduction rate is 82%, and the steel plate is placed into a furnace to be cooled to room temperature after the final rolling to obtain a plate blank;
(10) a heat treatment process: quenching at 840 deg.C for 30 min, and water quenching; tempering at 500 ℃, keeping the temperature for 120min, and air-cooling after tempering to obtain the steel plate;
(11) the room temperature tensile test was carried out on the sample to obtain the material mechanical properties shown in table 2.
TABLE 2
| Yield strength (MPa) | Tensile strength (MPa) | Elongation (%) |
| 1355 | 1430 | 15.1 |
Example 3:
(1) alloy chemical composition (mass percent): c: 0.09%, Si: 0.1%, Mn: 0.15%, Ni: 10.8%, Cr: 1.7%, Mo: 0.9%, V: 0.04%, Ti: 0.010%, Al: 0.06%, Nb: 0.07%, Co: 7.0 percent;
(2) heating and melting the steel alloy by using a vacuum melting and heating mode;
(3) the alloy smelting is carried out in an argon atmosphere;
(4) after the steel is completely melted, the steel is overheated to 50-100 ℃, after the liquid level is stable, Al-10 wt.% Ti composite stranded wire with the diameter of 2 mm is added after the oxygen content in the molten steel reaches 30 PPm, and the Al addition is 0.065 wt.% and the Ti addition is 0.007 wt.% through calculation;
(5) smelting under the protection of argon gas with the pressure of 0.5MPa, and pouring after Al-Ti composite stranded wires are melted and heat preservation is carried out for 3 min;
(6) pouring under the protection of argon gas with the pressure of 0.5MPa, wherein the linear velocity of flowing of the molten metal in the pouring process is not lower than 1.7 m/s;
(7) controlling the cooling speed in the solidification process to be not lower than 500 ℃/min;
(8) after the metal is completely solidified, obtaining a casting blank, sampling and carrying out structure analysis on the casting state, as shown in figure 1, and detecting that a large number of nano particles which are dispersedly distributed exist in the structure, as shown in figure 2;
(9) subsequently, controlled rolling and controlled cooling are carried out, heat preservation is carried out for 2 hours at 1250 ℃, 7 passes of rolling are carried out, the initial rolling temperature and the final rolling temperature are respectively 1200 ℃ and 900 ℃, the total rolling reduction rate is 82%, and the steel plate is placed into a furnace to be cooled to room temperature after the final rolling to obtain a plate blank;
(10) a heat treatment process: quenching at 850 deg.C for 40 min, and water quenching; tempering at 550 ℃, keeping the temperature for 60min, and air-cooling after tempering to obtain the steel plate;
(11) the room temperature tensile test was carried out on the sample to obtain the material mechanical properties shown in table 3.
TABLE 3
| Yield strength (MPa) | Tensile strength (MPa) | Elongation (%) |
| 1299 | 1217 | 15.0 |
Claims (5)
1. The in-situ nano-particle reinforced ultrahigh-strength steel for ocean engineering is characterized by comprising the following alloy chemical components in percentage by mass: c: 0.06-0.09%, Si: 0-0.1%, Mn: 0-0.15%, Ni: 9.0-11.0%, Cr: 1.5-2.0%, Mo: 0.8-1.0%, V: 0.03-0.04%, Ti: 0.006-0.010%, Al: 0.06-0.08%, Nb: 0.06-0.08%, Co: 7.0 to 8.0 percent.
2. The method for preparing the in-situ nanoparticle reinforced ultrahigh-strength steel for ocean engineering according to claim 1, wherein Al- (1.5-30) wt.% Ti composite twisted wire with phi of 0.5-3 mm is fed into a steel melt containing O with the concentration of 5-100 PPm by a wire feeding and stirring method, and then the steel melt is cooled at a speed of more than 500K/min and solidified; al above the melting point of the base alloy during solidification2O3And Ti3O5The precipitated phase is firstly precipitated, the nano crystal nucleus is rapidly carried away from the generated area by utilizing strong convection, the concentration gradient of the trace elements is destroyed, the dynamic and thermodynamic conditions required by growth cannot be achieved, the flow field, the concentration field and the force field of the melt are controlled, and a large amount of in-situ nano-phase Al which is dispersedly distributed is generated in the smelted material2O3And Ti3O5(ii) a The performance of the steel is further improved by a subsequent rolling and cooling control process and a heat treatment process.
3. The preparation method of the in-situ nanoparticle reinforced ultrahigh-strength steel for ocean engineering as claimed in claim 1 or 2, characterized by comprising the following specific processes:
(1) heating and melting the steel alloy by using a vacuum melting heating mode;
(2) after the steel is completely melted, overheating the steel by 50-100 ℃, measuring the oxygen content in the molten steel to be 5-100 PPm after the liquid level is stable, introducing argon into the furnace, and adding Al-Ti composite stranded wires with the diameter of 0.5-3 mm;
(3) under the protection of argon gas with the pressure of 0.01-0.5 MPa, alloy smelting is carried out, and pouring is carried out after Al-Ti composite stranded wires are melted and heat preservation is carried out for 1-5 min;
(4) pouring under the protection of argon at the pressure of 0.01-0.5 MPa, wherein the linear velocity of flowing of the molten metal in the pouring process is not lower than 1.7 m/s;
(5) controlling the cooling speed in the solidification process to be not lower than 500 ℃/min;
(6) obtaining a casting blank after the metal is completely solidified;
(7) subsequently, controlled rolling and controlled cooling are carried out, the total pass reduction is 70% -90% after multi-pass rolling, and the plate blank is placed into a furnace to be cooled to room temperature after final rolling to obtain a plate blank;
(8) performing water quenching and tempering, and then performing air cooling to obtain the steel plate; the yield strength of the steel is more than or equal to 1200MPa, and the elongation is more than or equal to 15%.
4. The method for preparing in-situ nanoparticle reinforced ultrahigh-strength steel for ocean engineering according to claim 3, wherein the controlled rolling and controlled cooling process in the step (7) is that the temperature is kept at 1200-1250 ℃ for 2h, and the temperature ranges of the initial rolling and the final rolling are 1150-1200 ℃ and 850-900 ℃ respectively through multi-pass rolling.
5. The method for preparing in-situ nanoparticle reinforced ultra-high strength steel for ocean engineering according to claim 3, wherein the water quenching temperature in the step (8) is as follows: 840 ℃ to 860 ℃, and the tempering temperature is 500 ℃ to 550 ℃.
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| CN113755760A (en) * | 2021-09-10 | 2021-12-07 | 北京科技大学 | In-situ nano reinforced and toughened crankshaft steel |
Citations (6)
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