CN111057958B - Corrosion-resistant, anti-irradiation and high-strength super ODS steel and preparation method thereof - Google Patents
Corrosion-resistant, anti-irradiation and high-strength super ODS steel and preparation method thereof Download PDFInfo
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- 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
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- 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
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0026—Matrix based on Ni, Co, Cr or alloys thereof
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- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
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Abstract
本发明属于先进核能结构钢技术领域，具体涉及一种耐腐蚀和高温、抗辐照、高强度的ODS钢及其制备方法。钢的成分范围(重量百分比)是Cr:12.0～16.0％；Al:3.0～5.0％；(W+Mo):1.0～1.5％；Y2O3:0.1～0.5％；Zr:0.1～0.5％；Fe余量。其它杂质元素含量如下：C≤0.02％；N≤0.02％；Co≤0.1％；Ni≤0.1％；Cu≤0.01％；P≤0.005％；S≤0.005％。在常规ODS钢基础上，通过成分设计优化，控制碳含量在母合金冶炼后达到0.005％以下、最终粉末冶金制备后0.02％以下，避免形成在高温、辐照条件下易于熟化的M23C6碳化物以提高高温稳定性和蠕变强度；通过协同控制Cr、Al含量形成致密氧化膜提高抗腐蚀氧化能力、并平衡时效或辐照脆性；通过纳米氧化物尺寸、数密度、种类等调控来提高抗辐照性能。基于以上特征，材料同时具有耐腐蚀(主要为液态金属等)和高温、高强度、抗辐照的优异性能。The invention belongs to the technical field of advanced nuclear energy structural steel, and particularly relates to a corrosion-resistant, high-temperature, radiation-resistant, high-strength ODS steel and a preparation method thereof. The composition range (weight percent) of steel is Cr: 12.0-16.0%; Al: 3.0-5.0%; (W+Mo): 1.0-1.5%; Y 2 O 3 : 0.1-0.5%; Zr: 0.1-0.5% ; Fe margin. The contents of other impurity elements are as follows: C≤0.02%; N≤0.02%; Co≤0.1%; Ni≤0.1%; Cu≤0.01%; P≤0.005%; S≤0.005%. On the basis of conventional ODS steel, through the optimization of composition design, the carbon content is controlled to be less than 0.005% after smelting the master alloy and less than 0.02% after the final powder metallurgy preparation, so as to avoid the formation of M 23 C 6 which is easy to mature under high temperature and irradiation conditions. Carbide to improve high temperature stability and creep strength; form a dense oxide film by synergistically controlling the content of Cr and Al to improve corrosion resistance and oxidation resistance, and balance aging or irradiation brittleness; through the regulation of nano-oxide size, number density, species, etc. Improve radiation resistance. Based on the above characteristics, the material has both corrosion resistance (mainly liquid metal, etc.) and excellent properties of high temperature, high strength, and radiation resistance.
Description
Technical Field
The invention belongs to the field of metal materials for corrosion-resistant, high-temperature-resistant and irradiation-resistant advanced nuclear energy systems, and particularly relates to Oxide Dispersion Strengthened steel (hereinafter referred to as super ODS steel) with special medium corrosion resistance, irradiation resistance and high strength and a preparation method thereof.
Background
China is actively developing advanced nuclear energy systems such as fourth generation fission reactors, accelerator driven subcritical systems (ADS), fusion reactors and the like. Compared with the existing fission reactor, the key core material of the future advanced nuclear energy system faces a more severe service environment and needs to meet the challenges of extreme environments such as higher temperature, stronger neutron irradiation, special medium corrosion and the like. The lead (bismuth) cold fast reactor (LFR) is one of six large reactors which are the long-term development targets in the international forum of the fourth generation of nuclear energy systems, is expected to become the first advanced nuclear energy system for realizing commercial application, and can be designed into a space reactor, a multipurpose movable small reactor and the like according to different purposes. An accelerator-driven subcritical transmutation system (ADS) is also listed in a novel nuclear energy system by an international atomic energy agency, and is a new way for exploring the sustainable development of nuclear fission energy. These advanced nuclear energy systems such as LFR and ADS use liquid lead and liquid lead bismuth eutectic alloys as cooling media. Therefore, the method not only meets the requirements of high temperature and irradiation performance, but also is suitable for the research and development of key materials of special media, and has very important significance and wide prospect.
Austenitic steel has been widely used in conventional nuclear reactors, but its radiation swelling problem is prominent, limiting its application space in advanced nuclear energy systems. Ferrite/martensite steel (F/M) has superior radiation resistance and thermophysical properties, but its creep strength is significantly reduced above 550 ℃. Oxide dispersion strengthened steel (ODS steel) has superior high-temperature mechanical properties and neutron irradiation resistance and other properties compared with structural materials for nuclei such as austenitic steel, ferrite/martensite steel and the like, is one of the most potential materials of an advanced nuclear energy system, and has become a hotspot in the international field of advanced nuclear material research. The excellent performance of ODS steel comes from two main aspects: on one hand, the dispersed and fine nanoscale precipitated phase has high thermal stability, is beneficial to improving the high-temperature creep strength, and improving the highest service temperature, thereby bringing better economic effect; on the other hand, the irradiation defect is captured to play a role of a trap, and the neutron irradiation resistance is enhanced.
In recent years, research and development of ODS steel have been greatly advanced. However, the existing ODS steel composition and structure design considering special medium corrosion, longer-term high-temperature and strong-irradiation multiple extreme service environments still has one-sidedness and disadvantages: (1) the physical and chemical actions of corrosive media such as liquid metal lead, bismuth and the like lead to the continuous reduction of the bearing area of the material and the influence on the structural stability on the one hand, and lead to the reduction of mechanical and physical properties on the other hand, so that the material fails in advance. However, the research and development of ODS steel materials at high temperature of 600 ℃ or above and in special medium service environments are extremely lacking, and the research belongs to the technical problem of international advanced science. (2) The conventional ODS steel contains certain carbon element in the components, and a large amount of M is formed23C6The carbide is easy to coarsen and grow under the condition of high-temperature long-service cooperative strong irradiation. And coarse M23C6Carbides are the major crack sources of creep rupture, leading to creep failure and a sharp increase in the ductile-to-brittle transition temperature (DBTT). (3) W, Mo element is a brittle Laves phase (Fe)2W、Fe2Mo) as a main element. The excessive W, Mo element content can increase the driving force of Laves phase precipitation, the curing speed is extremely high under the synergistic effect of high temperature and irradiation, and the solid solution strength of W, Mo element is reducedThe coarsened Laves phase also induced creep rupture, leading to an increase in DBTT.
Therefore, aiming at the unique corrosion problem and higher design requirements brought by the special medium of the advanced nuclear energy system, the component design is optimized on the basis of the existing ODS steel, and a novel super ODS steel material is developed, so that the material has high strength and super radiation resistance and meets the requirement of resisting the corrosion of the special medium.
Disclosure of Invention
The invention aims to provide corrosion-resistant, irradiation-resistant and high-strength ODS steel and a preparation method thereof.
The technical scheme of the invention is as follows:
the super ODS steel with corrosion resistance, radiation resistance and high strength comprises the following alloy components in percentage by weight:
Cr:12.0～16.0％；Al:3.0～5.0％；(W+Mo):1.0～1.5％；Y2O3: 0.1-0.5%; zr: 0.1-0.5%; the balance of Fe and other impurity elements; the contents of other impurity elements are as follows: c is less than or equal to 0.02 percent; n is less than or equal to 0.02 percent; co is less than or equal to 0.1 percent; ni is less than or equal to 0.1 percent; cu is less than or equal to 0.01 percent; p is less than or equal to 0.005 percent; s is less than or equal to 0.005 percent.
The super ODS steel with corrosion resistance, radiation resistance and high strength has a ferrite structure, the size of nano precipitated phase particles is less than 50nm, and the number density is 1022～24/m3An order of magnitude.
The preparation method of the corrosion-resistant, irradiation-resistant and high-strength super ODS steel comprises the following steps: purifying and smelting mother alloy → atomizing powder → high-energy mechanical ball milling → pumping powder sheath → curing and forming → hot forging → hot rolling → normalizing heat treatment to obtain stable structure; the master alloy comprises the following components in percentage by weight: cr: 12.0-16.0%; (W + Mo): 0.8-1.5%; al: 3.0-5.0%; zr: 0.1-0.5%; fe: the balance; the abbreviation is: Fe-0C- (12-16) Cr-1.5(W + Mo) - (3-5) Al- (0.1-0.5) Zr; in the purification smelting of master alloy, the content of impurity elements needs to be strictly controlled: c is less than or equal to 0.005 percent; n is less than or equal to 0.005 percent; ni is less than or equal to 0.1 percent; co is less than or equal to 0.1 percent; cu is less than or equal to 0.01 percent; p is less than or equal to 0.005 percent; s is less than or equal to 0.005 percent.
According to the preparation method of the corrosion-resistant, irradiation-resistant and high-strength super ODS steel, the requirements for powder atomization are as follows: the particle size of the powder is less than or equal to 150 mu m, the pressure of atomizing gas is more than or equal to 3.5MPa, and the powder atomization protective atmosphere is as follows: high purity argon gas with volume purity more than or equal to 99.99 percent.
In order to realize mechanical alloying and ensure that a nano precipitated phase is uniformly and dispersedly distributed in master alloy powder, the preparation method of the corrosion-resistant, irradiation-resistant and high-strength super ODS steel has the following technological parameters: the ball milling time is 40-80 h, the rotating speed is 300-500 r/min, the ball material mass ratio (5-20) is 1, and the ball milling protective atmosphere is as follows: high purity argon gas with volume purity more than or equal to 99.99 percent.
In the preparation method of the corrosion-resistant, irradiation-resistant and high-strength super ODS steel, in order to remove gas adsorbed on the surface in the powder ball milling process, reduce the porosity and improve the powder density, the powder after mechanical alloying is subjected to a sheath gas extraction process: the temperature is 300-500 ℃, the heat preservation time is 2-20 h, and the vacuum degree is not less than 10-1Pa。
The preparation method of the corrosion-resistant, irradiation-resistant and high-strength super ODS steel comprises the following steps of: the heat preservation temperature is 1000-1200 ℃, and the heat preservation time is 2-5 h.
In order to further improve the density and mechanical property of the solidified and formed material, the preparation method of the corrosion-resistant, irradiation-resistant and high-strength super ODS steel has the following control of the hot forging process: the forging temperature is 1000-1200 ℃, the finish forging temperature is 800-1000 ℃, and the forging ratio is 5: 1-10: 1.
The preparation method of the corrosion-resistant, irradiation-resistant and high-strength super ODS steel is used for further improving the density and mechanical property of the material and preparing the material into a plate or a pipe, and the hot rolling process is controlled as follows: the initial rolling temperature is 1000-1200 ℃, the final rolling temperature is 800-1000 ℃, and the rolling passes are 5-20 times.
In the preparation method of the corrosion-resistant, irradiation-resistant and high-strength super ODS steel, in order to eliminate stress and homogenize the structure, the normalizing heat treatment process is controlled as follows: and (3) air cooling at the temperature of 800-1200 ℃ after heat preservation for 0.5-2 h.
The design idea of the invention is as follows:
based on the great prospect and special background of the advanced nuclear energy development, the invention provides a design and a preparation method of novel super ODS steel, which is characterized in that: (1) the carbon content in the master alloy is controlled to be below 0.0050 wt% as much as possible, so that M which is easy to cure under high-temperature and irradiation conditions is not formed in the novel super ODS steel23C6Carbide, thereby improving the high-temperature long-term stability and the high-temperature creep strength; (2) by adding a proper amount of Al, a compact and stable alumina film is formed on the surface of the material, so that the high-temperature oxidation and corrosion resistance is improved, and the aim of protecting a matrix is fulfilled; (3) the proper content of Cr is designed, so that the corrosion performance is improved, and meanwhile, the aging and irradiation brittleness caused by forming a brittle alpha' phase due to overhigh Cr are avoided; (4) adding a proper amount of Zr alloy elements to refine the grain size and precipitated phase size of the ODS steel and make up for the strength reduction caused by the addition of Al; (5) after yttrium oxide is added and mechanical alloying is carried out, nano-scale oxide particles are introduced into a master alloy matrix, the number density of precipitated phases is increased, and high-temperature creep strength and strong neutron irradiation resistance are obtained.
One of the key points of the technology is as follows: precise control of the C element in the super ODS steel master alloy. In one aspect, M23C6The coarsening rate of the carbide is relatively remarkable, especially at high temperature above 700 ℃, as shown in fig. 1. Therefore, it is necessary to avoid M23C6Is performed. On the other hand, M23C6The reduction or elimination of (b) can be achieved by controlling the carbon content. It has been found that when the carbon content is controlled below 0.02 wt%, the high temperature creep property of the material can be greatly improved, as shown in fig. 2. Therefore, the content of C in the master alloy components of the super ODS steel is regulated to be less than 0.005 wt%, so that the condition that the final carbon content is not more than 0.02 wt% due to pollution rise of the carbon content in the ball milling process can be avoided, and M easy to coarsen under the conditions of long-term high temperature and irradiation service is avoided23C6(M is mainly Cr, Fe) carbideAnd a precipitated phase is formed, so that an excellent high-temperature thermal stability structure is obtained, and the creep property and the irradiation resistance are improved.
The second key point of the technology is that: controlling the content range of Cr and Al. As the Cr content increases, the corrosion resistance increases, but at the same time the brittleness increases. When the Cr content exceeds 16 wt%, aging brittleness and irradiation brittleness are significantly increased due to easy formation of α' phase, as shown in fig. 3. The ferrite structure is obtained by controlling the Cr content to be more than or equal to 12 wt%, the corrosion resistance and the strength are improved, the Cr content is controlled to be less than or equal to 16 wt%, and the brittleness caused by the precipitation of a Cr-rich phase (alpha') under the conditions of long-term aging and irradiation is avoided. The increase in Al content is advantageous in improving corrosion resistance by forming a dense oxide film, but also brings about a decrease in material strength and workability. By controlling the Al content to be 3-5 wt%, a surface compact oxide film is formed, the corrosion resistance and oxidation resistance of the liquid lead bismuth are improved, and the self-repairing function is achieved. Therefore, the Cr content of the present invention is 12 to 16 wt%, and Al is 3 to 5 wt%.
The third key point of the technology is that: by controlling the nitrogen content in the master alloy to be below 0.005 wt% and the nitrogen content after the final powder is prepared to be below 0.02 wt%, the formation of CrN and AlN inclusion or coarse precipitated phases is avoided.
The invention has the advantages and beneficial effects that:
1. on the basis of the existing ODS steel, through component design optimization, the carbon content is controlled to be below 0.0050% after smelting of master alloy and below 0.02% after final powder metallurgy preparation as far as possible, and M easy to coarsen under the conditions of high temperature and irradiation is prevented from being formed23C6Carbide, and a compact oxide film is formed by cooperatively controlling the contents of Cr and Al, so that the corrosion resistance and oxidation resistance are improved, and the synchronous improvement of the strength, the irradiation resistance and the corrosion resistance is realized.
2. Patent document 1 (publication No. CN105274445A) relates to an oxide dispersion strengthened steel and a method for producing the same, which gives that a certain amount of nano yttrium oxide Y is added to the steel2O3And Ti particles to achieve strengthening and radiation resistance properties. The preparation method is similar to the application in all parameters, but the two parameters are obviously different: patent document1 contains a certain C element to form M23C6A carbide precipitated phase; the content of C element in the alloy system of the invention is extremely low; in patent document 1, micro-alloying elements Ta and V are further added, and the high-temperature mechanical properties and high-temperature structural stability are further improved by the precipitated phases formed thereby, whereas in the present invention, in addition to the nano precipitated phase, M with a large high-temperature aging rate is strictly controlled23C6The long-term high-temperature creep property of the alloy is improved; patent document 1 emphasizes the low activation characteristic of ODS steel, whereas the composition of super ODS steel in the present invention does not emphasize the low activation characteristic, but encompasses the low-activation ODS steel composition (achieved by composition trimming).
3. Patent document 2 (publication No. CN108893580A) relates to a nitride and oxide co-dispersion strengthened ODS steel and a method for producing the same, in which each parameter is similar to that of the present application. First, however, the two alloy systems are different: although the carbon content is also strictly controlled in both alloy systems, patent document 2 discloses adding an appropriate amount of nitrogen while controlling carbon to form nitride (MX) instead of carbide (M)23C6) In the alloy system, the contents of carbon and nitrogen are simultaneously controlled, so that the inclusion or precipitation phase of carbide and other nitrides is avoided; the nanophase precipitated phase in patent document 2 is mainly Y2O3In the present invention, the precipitate phase is a complex precipitate phase of Y-Al-O or Y-Zr-O. Secondly, the two main performance advantages and the targeted service environments are different: patent document 2 aims to improve high-temperature stability and radiation resistance simultaneously, and does not address a special corrosive environment. The invention also adds a proper amount of Al to form a compact oxidation film to protect the matrix by cooperating with the regulation and control of Cr content while giving consideration to high-temperature strength and radiation resistance, thereby improving the corrosion and oxidation resistance.
Drawings
FIG. 1 shows the structural evolution of 9Cr-ODS steel containing 0.1 wt% C at 700 ℃ before and after 10000h thermal aging test. Wherein (a) before aging, and (b) after 700 ℃/10000h aging. In the figure, the white particles are M23C6The dimensional change before and after aging is significant.
Fig. 2 is a graph of the relationship of carbon content in heat resistant steel to creep rupture time, minimum creep rate (650 ℃/140MPa), see document f.abe, sci.tech.adv.mater.vol.,9,2008,013002. In the figure, Carbon concentration on the abscissa represents the Carbon content (wt%), Time to failure on the ordinate represents the creep rupture Time (h), and Minimum creep rate on the ordinate (right) represents the Minimum creep rate (1/h).
FIG. 3 is a graph showing the relationship between the room temperature absorption energy and Cr content of ODS steel aged at 500 ℃ to 10000h, see document A. Kimura, J.Nucl. Mater., Vol 417,2011, 176-179. In the figure, the abscissa Cr concentration represents the chromium content (wt%), and the ordinate Absorbed Energy at RT represents the room temperature absorption Energy (J).
FIG. 4 is a microstructure characterization of the super ODS steel in example 1. Wherein, (a) is SEM photograph of crystal grain morphology, and (b) is TEM photograph of nano oxide.
FIG. 5 shows the corrosion morphology of the super ODS steel in example 1 after 2000h corrosion in static oxygen-free liquid lead-bismuth at 600 ℃. Wherein (a) the surface is etched, and (b) the cross section is etched.
FIG. 6 shows the corrosion morphology of the super ODS steel in example 1 after 500h corrosion in static oxygen-free liquid lead-bismuth at 700 ℃. Wherein (a) the surface is etched, and (b) the cross section is etched.
FIG. 7 is an EDS composition analysis of the cross-sectional oxide layer of the super ODS steel of example 1 after etching for 500 hours in static oxygen-free liquid lead bismuth at 700 ℃. Wherein, (a) SEI morphology, (b) element Al, and (c) element O.
Fig. 8 is the microstructure of example 3. Wherein, (a) the distribution of inclusions; (b) EDS analysis of precipitated phase.
FIG. 9 shows the corrosion morphology of the super ODS steel master alloy (FeCrAl) in comparative example 1 after 1000h corrosion in liquid lead bismuth with static saturated oxygen at 600 ℃. Wherein (a) the surface is etched, and (b) the cross section is etched.
FIG. 10 shows the formation of TiC or Ti (CO) inclusions in 12Cr-ODS steel, see Yanfen Li, et al, Materials Science & Engineering A654 (2016) 203-212. Wherein, (a) SEI morphology, (b) element Ti, (C) element C, and (d) element O.
FIG. 11 shows the corrosion microstructure of 9Cr-ODS steel after exposure to static, oxygen-controlled liquid lead conditioning at 600 ℃/250h, see the document Yanfen Li, et al, Journal of Nuclear Materials 443(2013) 200-. Wherein, (a) surface topography; (b) the section appearance, the main alloy element changes with the corrosion depth; (c) the cross section appearance shows a decarburized layer, a carbide-poor layer and a carbide-rich layer.
FIG. 12 is the cross-sectional morphology of the oxide film of SIMP steel and T91 steel after corrosion for 100 and 500 hours in static saturated lead bismuth oxide at 600 ℃, which is shown in the literature: poplar et al, journal of metals, Vol 52(10), 2016: 1207-. Wherein (a) and (b) are SIMP steels; (c) and (d) is T91 steel.
FIG. 13 shows the microstructure of SIMP steel after corrosion in static saturated lead bismuth oxide at 600 ℃ for 2000 h. Wherein, (a) the surface morphology, and (b) the cross-sectional morphology.
Detailed Description
In the specific implementation process, the super ODS steel has the composition range of 12.0-16.0% of Cr; 3.0 to 5.0 percent of Al; 1.0 to 1.5% of (W + Mo); y is2O3: 0.1-0.5%; zr: 0.1-0.5%; the balance being Fe and other impurity elements. The contents of other impurity elements are as follows: c is less than or equal to 0.02 percent; n is less than or equal to 0.02 percent; co is less than or equal to 0.1 percent; ni is less than or equal to 0.1 percent; cu is less than or equal to 0.01 percent; p is less than or equal to 0.005 percent; s is less than or equal to 0.005 percent.
The preparation method of the super ODS steel comprises the following steps:
(1) according to the weight percentage, smelting a pure and purified master alloy by adopting a vacuum induction smelting method: Fe-0C- (12-16) Cr-1.5(W + Mo) - (3-5) Al- (0.1-0.5) Zr. Wherein, in order to control the carbon content, high-purity raw materials such as high-purity iron, Cr, W and the like are adopted for vacuum induction melting. The carbon content in the components is reduced to an extremely low level (less than or equal to 0.005 percent); the content of (W + Mo) is controlled below 1.5 percent to slow down the Laves phase precipitation of the steel in the long-term high-temperature service process. The contents of other impurity elements are controlled as follows: c is less than or equal to 0.005 percent; n is less than or equal to 0.005 percent; co is less than or equal to 0.1 percent; ni is less than or equal to 0.1 percent; cu < 0.01%; s is less than or equal to 0.005 percent; p is less than or equal to 0.005 percent.
(2) The gas atomization powder preparation process of the master alloy Fe-0C- (12-16) Cr-1.5(W + Mo) - (3-5) Al- (0.1-0.5) Zr comprises the following steps: the particle size is less than or equal to 150 microns (preferably 100 microns), the atomizing gas pressure is more than or equal to 3.5MPa (preferably 4MPa), the superheat degree is more than or equal to 200 ℃ (preferably 200 ℃), and the protective gas atmosphere is 99.99% argon.
(3) Mechanical ball milling to realize alloying technological parameters: the ball material mass ratio is (5-20): 1, the ball milling time is 40-80 h, the rotating speed is 300-500 r/min, and the ball milling atmosphere is argon with the volume purity of 99.99%.
(4) The technological parameters of mechanical alloying powder air extraction are as follows: sealing the powder by using a sheath, degassing, keeping the temperature at 300-500 ℃ for 2-20 h, and keeping the vacuum degree not lower than 10-1Pa。
(5) The curing and forming process parameters of the powder sheath are as follows: the heat preservation temperature is 1000-1200 ℃, and the heat preservation and pressure maintaining time is 2-5 h.
(6) The hot forging process is controlled as follows: the forging temperature is 1000-1200 ℃, the finish rolling temperature is 800-1000 ℃, and the forging ratio is 3: 1-10: 1.
(7) The hot rolling process is controlled as follows: the initial rolling temperature is 1000-1200 ℃, the final rolling temperature is 800-1000 ℃, and the rolling passes are 5-20.
(8) The heat treatment process of the ODS steel rolled plate or pipe comprises the following steps: the normalizing process parameter is 800-1200 ℃/1 h/air cooling.
Hereinafter, the present invention will be described in detail by way of examples and comparative examples.
The steel systems of examples 1-3 were prepared by the same powder metallurgy method, but with different control of carbon and nitrogen contents; the comparative steel system includes the master alloy, conventional ODS steel, and liquid metal corrosion resistant ferrite/martensite steel referred to in the present invention. The differences in microstructure, corrosion resistance and tensile properties thereof were comparatively analyzed by the example steels and the comparative steels.
Example 1:
in this example, the super ODS steel had alloy compositions of Cr 13.50%, W1.02%, Al 3.45%, Zr 0.28%, Y2O30.29 percent of C, 0.017 percent of N, 0.0054 percent of Cu, 0.008 percent of P, 0.003 percent of S, 0.002 percent of Co, 0.035 percent of Ni, 0.042 percent of Fe and the balance of Fe.
The preparation process of the super ODS steel is as follows:
(1) and (3) purifying and smelting the master alloy: cr and Al elements in the master alloy are elements easy to burn and damage, and the materials are required to be prepared according to the yield of 90-95%. Ultra-pure iron, W and Cr with very low C content were used for tight control of the carbon content. The test components of the master alloy after vacuum smelting are as follows: 13.80Cr-1.02W-4.05Al-0.31 Zr-0.0012C.
(2) Powder atomization: the pressure of atomizing gas is 4.0MPa, the degree of superheat is 250 ℃, and the protective atmosphere is argon with the volume purity of 99.99 percent. And carrying out next high-energy mechanical ball milling on the atomized powder with the granularity less than or equal to 150 mu m.
(3) Mechanical alloying: to make Y about 50nm in particle diameter2O3The particles are dissolved in the Fe-based alloy in a solid manner and are uniformly dispersed and distributed, and mechanical alloying is realized by adopting high-energy ball milling. The technological parameters are controlled as follows: the ball milling atmosphere is argon with the volume purity of 99.99 percent, the ball material mass ratio is 10:1, the ball milling time is 40h, and the rotating speed is 350 r/min.
(4) Sealing and degassing: encapsulating the powder in a sheath and removing adsorbed gas from the surface of the powder particles to reduce porosity. The air extraction process comprises the following steps: the vacuum degree is 0.1Pa, the temperature is 300 ℃, and the time is 4 h.
(5) Curing and forming: and (4) performing solidification forming by using hot isostatic pressing. The heat preservation temperature and pressure are 1150 ℃/100MPa, and the time is 4 h;
(6) hot forging: the forging temperature is 1100 ℃, the finish forging temperature is 800 ℃, and the forging ratio is as follows: 5:1.
(7) Hot rolling: the initial rolling temperature is 1100 ℃, the final rolling temperature is 800 ℃, and the rolling ratio is as follows: 5:1.
(8) And (3) heat treatment: 900 ℃/60 min/air cooling.
As shown in fig. 4, a photograph of microstructure analysis after powder metallurgy preparation in example 1. It is shown that the crystal grains are elongated in the rolling direction and the diameter of the crystal grains is about 1 to 2 μm in the width method. Under TEM analysis, the matrix is dispersed with high volume fraction nanometer oxide with size of 10 nm.
FIGS. 5 to 7 are microscopic analyses of the super ODS steel of example 1 after static oxygen-independent corrosion of the liquid metal, lead-bismuth.
As shown in fig. 5, a microscopic morphology photograph after high temperature corrosion at 600 ℃ for 2000 h. The color of the surface of the sample is slightly darkened after corrosion, and the thickness of the corrosion layer displayed on the section is within 10 mu m, which shows that the super ODS steel has excellent liquid metal lead bismuth corrosion resistance.
As shown in fig. 6, a microscopic morphology photograph after 500h of high temperature 700 ℃ etching. The results show that the temperature is raised to 700 ℃, and the thickness of the corrosion layer is thinner than that of 600 ℃ in most regions after 500 hours of corrosion, which is mainly caused by Al2O3Formation of the protective layer (fig. 7).
Example 2:
in this example, the alloy components of the super ODS steel were 13.55% Cr, 1.01% W, 4.05% Al, 0.25% Zr, and Y2O30.30 percent of C, 0.050 percent of N, 0.008 percent of Cu, 0.009 percent of Cu, 0.005 percent of P, 0.005 percent of S, 0.026 percent of Co, 0.037 percent of Ni and the balance of Fe. The composition differs from example 1 mainly in that: the carbon content is not strictly controlled.
The super ODS steel was prepared as in example 1.
Example 3:
in this example, the alloy components of the super ODS steel were 13.85% Cr, 1.05% W, 3.85% Al, 0.30% Zr, and Y2O30.32 percent of C, 0.015 percent of N, 0.1 percent of Cu, 0.009 percent of Cu, 0.005 percent of P, 0.005 percent of S, 0.063 percent of Co, 0.027 percent of Ni and the balance of Fe. The composition differs from example 1 mainly in that: carbon is strictly controlled but nitrogen content is high due to atmospheric pollution.
The super ODS steel was prepared as in example 1.
FIG. 8 is a microscopic topography analysis of example 3. Because of the pollution of nitrogen in the powder preparation process, a large amount of AlN or Al is formed in the alloy2O3The performance of the alloy is affected.
Comparative example 1: example 1 Master alloy FeCrAl
The master alloy comprises the following components: 13.80Cr-1.02W-4.05Al-0.31 Zr-0.0012C. The pure smelting master alloy was cut out and subjected to the same forging, rolling and heat treatment as in example 1 without pulverization and mechanical ball milling.
As shown in FIG. 9, the microscopic analysis of the master alloy FeCrAl steel after being corroded for 1000h at 600 ℃ by static oxygen-free liquid metal lead bismuth shows that the thickness of the corrosion layer reaches about 50 μm on the cross section. Whereas the super ODS steel has a thickness of about 10 μm after 600 ℃/2000h corrosion. The results further demonstrate that the super ODS steel has better liquid metal lead bismuth corrosion resistance than the master alloy FeCrAl.
Comparative example 2: 12Cr-ODS ferritic steel without strict control of carbon
The 12Cr-ODS steel was prepared by a preparation process of "master alloy smelting-powder atomization-mechanical alloying-seal air extraction-solidification molding-hot forging-hot rolling" similar to that of example 1. The alloy comprises the following components: 12.01Cr-1.91W-0.25Y2O3-0.31 Ti-0.033C-0.008N. The heat treatment process comprises the following steps: 1050 deg.C/60 min/air cooling.
As shown in FIG. 10, the microstructure of 12 Cr-ODSS steel was analyzed. The carbon content, although controlled to some extent, is 0.033% carbon, which, due to the strong bonding force of Ti and C, forms small amounts of TiC or Ti (co) inclusions, which inevitably affects the long-term service safety. Therefore, to avoid the formation of inclusions and M23C6The precipitated phase, the carbon content, is strictly controlled in inventive example 1.
Comparative example 3: liquid lead-lithium corrosion resistance of 9Cr-ODS martensitic steel
The 9Cr-ODS steel was prepared by a preparation process of "master alloy smelting-powder atomization-mechanical alloying-seal air extraction-solidification molding-hot forging-hot rolling" similar to that of example 1. The alloy comprises the following components: 9.08Cr-1.97W-0.14C-0.29Y2O3-0.23 Ti-0.013N. The heat treatment process comprises the following steps: 1050 ℃/60 min/air cooling +800 ℃/60 min/air cooling.
Comparative example 3 belongs to nano-oxide reinforced ODS steel as well as the present invention. However, since the Cr content in the alloy is only about 9% slightly lower and no Al or Si element is added, the liquid metal corrosion resistance is insufficient. As shown in FIG. 11, the microstructure of the 9Cr-ODS steel after exposure to static, oxygen-controlled liquid lead conditioning was 600 ℃/250 h. The results show that the surface oxide film is not sufficient to block corrosion of the liquid metal along grain or subgrain boundaries, while the surface is depleted of Cr and carbides decompose due to Cr dissolution. The corrosion resistance of the 9Cr-ODS steel will be further reduced in a long-term, higher temperature corrosive environment. It can be seen that the corrosion resistance of the 9Cr-ODS steel, to which no other alloying elements for corrosion resistance are added, is to be further improved.
Comparative example 4: liquid lead bismuth corrosion resistance of SIMP steel added with Si and not added with Al
The SIMP steel is ferrite/martensite steel with Chinese proprietary intellectual property rights developed aiming at liquid metal lead bismuth resistance, high temperature resistance and radiation resistance of an accelerator driven subcritical system (ADS). SIMP steels improve the resistance to liquid metal corrosion by adding a suitable amount of the low activating element Si to the alloy instead of the activating element Al. The components are 10.25Cr-1.45W-0.22C-0.52Mn-0.15V-0.12Ta-1.22 Si-0.002N. The SIMP steel is manufactured using vacuum purification smelting, followed by hot forging, hot rolling process, etc. similar to example 1. The heat treatment process comprises the following steps: 1050 ℃/60 min/air cooling +780 ℃/60 min/air cooling.
As shown in FIG. 12, after the SIMP steel added with a certain amount of Si is subjected to static and uncontrolled-oxygen liquid lead-bismuth corrosion for 100 and 500 hours at the temperature of 600 ℃, the corrosion layer depth is far less than that of T91 steel not added with Si, and the SIMP steel has excellent liquid lead-bismuth corrosion resistance.
Further, the etching time was prolonged to 2000 hours, and as shown in FIG. 13, the SIMP steel began to have a nodular structure, and the depth of the etched layer reached about 100. mu.m. Compared with the corrosion test results of the super ODS steel in example 1 of the present invention (FIG. 5), it is shown that the liquid lead bismuth corrosion resistance of the SIMP steel is still weaker than that of the super ODS steel with Al added thereto according to the present invention.
Table 1 shows the yield strengths and tensile strengths of example steels and comparative steels within the composition range of the present invention. The steel of examples 1, 2 and 3 has the same preparation process and heat treatment schedule, but has different carbon and nitrogen content control. From the experimental results, it is understood that in example 1, contamination of carbon and nitrogen contents was strictly controlled, and a more desirable tensile strength was obtained. Example 2 has a slightly higher carbon content than example 1, and the strength is reduced because of the formation of a small amount of coarse inclusions such as carbides. In example 3, the carbon content was controlled, but the tensile strength was the lowest because a large amount of coarse AlN inclusions were formed due to contamination with nitrogen.
Comparative example 1 is the master alloy FeCrAl of example 1. Since no further nano-oxide addition provides dispersion strengthening, fine grain strengthening, the grains of comparative example 1 are coarse and the tensile strength is much lower than that of the ODS steel of example 1.
The tensile properties test results in the above table also show that the strength of the ODS steel with the nano precipitated phase introduced by mechanical alloying (e.g., comparative examples 2 and 3) is greatly improved as compared with the master alloy of example 1 of the present invention (comparative example 1) and other ferrite/martensite steels (e.g., comparative example 4), and the radiation resistance is expected to be greatly increased.
TABLE 1 yield and tensile Strength at Room temperature for the examples and comparative steels
| Yield strength sigma0.2(MPa) | Tensile Strength σb(MPa) | |
| Example 1 | 915 | 1058 |
| Example 2 | 716 | 929 |
| Example 3 | 663 | 827 |
| Comparative example 1 | 364 | 502 |
| Comparative example 2 | 1040 | 1154 |
| Comparative example 3 | 1035 | 1233 |
| Comparative example 4 | 613 | 833 |
The results of the examples show that the super ODS steel of the invention is mainly characterized in that: 1) the carbon and nitrogen content in the steel is extremely low (C: less than 0.02 percent; n: less than 0.02%), and the carbide M which is easy to coarsen and grow for a long time and at high temperature is avoided from forming in the matrix structure23C6(M is mainly Cr and Fe), and an inclusion or coarse precipitated phase such as CrN and AlN; 2) adding a proper amount of Al into the steel to form a compact oxide film so as to protect the corrosion resistance and the oxidation resistance of a matrix at high temperature; 3) the Cr content in the steel is controlled within a certain range, so that the corrosion resistance is ensured, the strength reduction caused by the addition of Al is improved, and the long-term aging brittleness or irradiation brittleness caused by a large amount of generated alpha '(alpha') phase is avoided; 4) the size of high-stability nano precipitated phase in the steel is within 50nm, and the number density (per cubic meter) is 1022～1024Order of magnitude to improve high temperature creep property and radiation resistance; 5) the contents of Co, W and Mo in the steel are limited to a lower level so as to reduce the precipitation driving force of the Laves phase of the steel under the long-term high-temperature condition. Based on the characteristics, the material has excellent performances of corrosion resistance (mainly liquid metal and the like) and high temperature, high strength and irradiation resistance.
Claims (8)
1. The corrosion-resistant, radiation-resistant and high-strength super ODS steel is characterized by comprising the following alloy components in percentage by weight:
Cr:12.0～16.0％；Al:3.45～5.0％；(W+Mo):1.0～1.5％；Y2O3: 0.1-0.5%; zr: 0.1-0.28%; the balance of Fe and other impurity elements; the contents of other impurity elements are as follows: c is less than or equal to 0.02 percent; n is less than or equal to 0.02 percent; co is less than or equal to 0.1 percent; ni is less than or equal to 0.1 percent; cu is less than or equal to 0.01 percent; p is less than or equal to 0.005 percent; s is less than or equal to 0.005 percent;
the super ODS steel has a ferrite structure, nano precipitated phase particles with a size below 50nm and a number density of 1022～24/m3An order of magnitude;
the preparation method of the corrosion-resistant, irradiation-resistant and high-strength super ODS steel comprises the following steps: purifying and smelting mother alloy → atomizing powder → high-energy mechanical ball milling → pumping powder sheath → curing and forming → hot forging → hot rolling → normalizing heat treatment to obtain stable structure; a vacuum induction smelting method is adopted to smelt a purified master alloy, and the master alloy comprises the following components in percentage by weight: cr: 12.0-16.0%; (W + Mo): 0.8-1.5%; al: 3.45-5.0%; zr: 0.1-0.28%; fe: the balance; the abbreviation is: Fe-0C- (12-16) Cr-1.5(W + Mo) - (3.45-5) Al- (0.1-0.28) Zr; in the purification smelting of master alloy, the content of impurity elements needs to be strictly controlled: c is less than or equal to 0.005 percent; n is less than or equal to 0.005 percent; ni is less than or equal to 0.1 percent; co is less than or equal to 0.1 percent; cu is less than or equal to 0.01 percent; p is less than or equal to 0.005 percent; s is less than or equal to 0.005 percent.
2. The corrosion-resistant, radiation-resistant, high-strength super ODS steel as claimed in claim 1, wherein the powder atomization is as follows: the particle size of the powder is less than or equal to 150 mu m, the pressure of atomizing gas is more than or equal to 3.5MPa, and the powder atomization protective atmosphere is as follows: high purity argon gas with volume purity more than or equal to 99.99 percent.
3. The corrosion-resistant, radiation-resistant and high-strength super ODS steel of claim 1, wherein in order to achieve mechanical alloying and to make the nano-sized precipitated phases uniformly and dispersedly distributed in the master alloy powder, the high-energy mechanical ball milling process parameters are as follows: the ball milling time is 40-80 h, the rotating speed is 300-500 r/min, the ball material mass ratio (5-20) is 1, and the ball milling protective atmosphere is as follows: high purity argon gas with volume purity more than or equal to 99.99 percent.
4. The corrosion-resistant, radiation-resistant and high-strength super ODS steel of claim 1, wherein, in order to remove gas adsorbed on the surface during the powder ball milling process, reduce porosity, increase powder compactness, a jacket air extraction process is performed on the mechanically alloyed powder: the temperature is 300-500 ℃, the heat preservation time is 2-20 h, and the vacuum degree is not less than 10-1Pa。
5. The corrosion-resistant, radiation-resistant, high-strength super ODS steel of claim 1, characterized in that the solidification-forming process of the alloyed powders is as follows: the heat preservation temperature is 1000-1200 ℃, and the heat preservation time is 2-5 h.
6. The corrosion-resistant, radiation-resistant and high-strength super ODS steel of claim 1, wherein, in order to further improve the compactness and mechanical properties of the solidified and formed material, the hot forging process is controlled as follows: the forging temperature is 1000-1200 ℃, the finish forging temperature is 800-1000 ℃, and the forging ratio is 5: 1-10: 1.
7. The corrosion-resistant, radiation-resistant and high-strength super ODS steel according to claim 1, characterized in that, in order to further improve the compactness and mechanical properties of the material and to prepare the material into plate or tube, the hot rolling process is controlled as follows: the initial rolling temperature is 1000-1200 ℃, the final rolling temperature is 800-1000 ℃, and the rolling passes are 5-20 times.
8. The corrosion-resistant, radiation-resistant, high-strength super ODS steel as set forth in claim 1, wherein the normalizing heat treatment process is controlled as follows in order to eliminate stress and homogenize the structure: and (3) air cooling at the temperature of 800-1200 ℃ after heat preservation for 0.5-2 h.
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| CN112941407B (en) * | 2021-01-27 | 2022-07-01 | 中国核动力研究设计院 | Nano-oxide reinforced ferrite steel for reactor, pipe and preparation method thereof |
| CN113936817B (en) * | 2021-10-14 | 2024-03-22 | 中国科学院合肥物质科学研究院 | Fusion reactor cladding flow passage structure with tritium resistance and corrosion resistance functions |
| CN114134429A (en) * | 2021-12-03 | 2022-03-04 | 中国核动力研究设计院 | ODS ferrite stainless steel fuel cladding tube and preparation method thereof |
| CN114921714B (en) * | 2022-06-06 | 2022-10-14 | 大连理工大学 | Y 2 O 3 Nano-particle dispersion strengthened steel and preparation method thereof |
| WO2024144738A1 (en) * | 2022-12-28 | 2024-07-04 | Selcuk Universitesi | Creep-resistant and microstructure-stable chromium-molybdenum and/or chrome-tungsten steels containing ytrium(iii) oxide and the production method of these steels |
| CN117403138B (en) * | 2023-10-24 | 2024-05-14 | 上海交通大学 | A corrosion-resistant oxide dispersion-strengthened steel and a method for preparing the same |
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