CN117123789B - Preparation method of heat-resistant and radiation-resistant ultrafine-grained martensitic steel - Google Patents
Preparation method of heat-resistant and radiation-resistant ultrafine-grained martensitic steelInfo
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- CN117123789B CN117123789B CN202311106275.9A CN202311106275A CN117123789B CN 117123789 B CN117123789 B CN 117123789B CN 202311106275 A CN202311106275 A CN 202311106275A CN 117123789 B CN117123789 B CN 117123789B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/10—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying using centrifugal force
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
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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
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- 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
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
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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
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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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
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Abstract
本发明公开了一种耐热抗辐照超细晶粒马氏体钢的制备方法，属于金属结构材料领域。该制备方法主要步骤包括：以低活化马氏体钢为母材雾化制备球形原料粉末，用溶胶凝胶法合成Sc4Zr3O12陶瓷氧化物粉末替代传统氧化物弥散强化钢(ODS)制备中添加的Y2O3和Ti粉末；以高能球磨和放电等离子烧结制备具有超细晶粒组织的ODS钢，再通过特殊热处理工艺获得马氏体组织。与传统ODS钢和马氏体钢的制备工艺相比，该方法不需要复杂的热机械处理工艺，即可获得晶粒细小的马氏体组织。材料室温抗拉强度达到1000‑1200MPa，同时拥有16‑20％的伸长率，且在650℃时其高温强度达到280‑320MPa。
The present invention discloses a method for preparing heat-resistant and radiation-resistant ultrafine-grained martensitic steel, which belongs to the field of metal structural materials. The main steps of the preparation method include: using low-activated martensitic steel as the base material to prepare spherical raw material powder by atomization, synthesizing Sc4Zr3O12 ceramic oxide powder by sol-gel method to replace Y2O3 and Ti powder added in the preparation of traditional oxide dispersion strengthened steel ( ODS ); preparing ODS steel with ultrafine grain structure by high-energy ball milling and spark plasma sintering, and then obtaining martensitic structure through special heat treatment process. Compared with the preparation process of traditional ODS steel and martensitic steel, this method does not require complex thermomechanical treatment process to obtain fine-grained martensitic structure. The material has a room temperature tensile strength of 1000-1200MPa, an elongation of 16-20%, and a high temperature strength of 280-320MPa at 650°C.
Description
Technical Field
The invention relates to a high-temperature-resistant and radiation-resistant metal structure material for a fission reactor and a fusion reactor, and particularly provides a preparation method of heat-resistant and radiation-resistant superfine grain martensitic oxide dispersion strengthening steel.
Background
Oxide Dispersion Strengthened (ODS) steel is considered as one of important candidate structural materials in nuclear reactors because of its excellent high temperature creep and irradiation resistance. The excellent performance of ODS steel benefits from the dispersed distribution of high-density nano oxides, the nano oxides can prevent grain growth and dislocation migration, the mechanical performance of the material is effectively improved, helium bubbles generated by neutron irradiation can be effectively captured at the interface between the nano oxides and a matrix, and the irradiation swelling problem of the material can be improved.
The properties of ODS steel depend mainly on the nature of the oxide and the matrix structure. The oxide added mainly is Y 2O3 at first, which has high melting point and anti-radiation performance, but single Y 2O3 phase is easy to coarsen at high temperature, the strengthening effect is limited, and then researchers find that ternary oxide phases with smaller size can be generated by adding the oxygen-related elements such as Ti, si, zr and the like into ODS steel, so that the performance of the material is improved, and a good foundation is laid for regulating and controlling the structural performance of the ODS steel. The ODS steel facing the fusion reactor at home and abroad at present is mainly 9Cr-ODS steel, such as European ODS-Eurofer steel, domestic ODS-CLF and the like. Unlike the ferrite ODS alloy of high Cr content, the 9Cr-ODS steel retains the matrix composition of the conventional heat-resistant martensitic steel because the low Cr content can prevent the irradiation hardening of the material and the martensitic structure has better impact resistance and irradiation resistance than the polygonal ferrite structure. For traditional heat-resistant martensitic steels, the martensitic structure is obtained by cooling in air through common heat treatment processes (i.e. normalizing and tempering). However, the following problems still remain in the preparation of 9Cr-ODS steel:
1) The addition of nano oxide in 9Cr-ODS steel can prevent the formation of martensite, because nano has extremely high pinning effect relative to grain boundary, in an austenitizing temperature region (950-1200 ℃), the phase transformation driving force of partial ferrite to austenite transformation is insufficient to overcome the zener pinning force of nano particles, so that compared with the traditional heat-resistant martensitic steel, the high-temperature structure of the 9Cr-ODS steel is usually austenite and residual ferrite, and the complete martensitic structure is difficult to obtain through common heat treatment process;
2) The irradiation resistance of the nano phase is also very important for engineering application of 9Cr-ODS steel, and researches show that the common nano precipitated phase is easy to amorphize under high-temperature irradiation, so that the crystal structure characteristics of the nano phase are lost, and therefore, the added nano oxide needs to be ensured to have a more stable structure.
Disclosure of Invention
In view of the above, the invention provides a preparation method of heat-resistant and irradiation-resistant ultrafine grain martensitic steel, which can effectively improve the heat resistance and irradiation resistance of ODS steel.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A heat-resistant and radiation-resistant superfine grain martensitic steel is prepared from atomized spherical powder and Sc 4Zr3O12 oxide powder through mixing, ball grinding, spark plasma sintering and heat treatment.
The invention provides a preparation method of heat-resistant and irradiation-resistant ultrafine grain martensitic steel, which comprises the following steps of performing high-energy ball milling on selected martensitic steel atomized powder and oxide powder, wherein the atomized powder comprises 8.5-9.5wt.% of Cr, 1-2 wt wt.% of W, 0.3-0.6 wt.% of Mn, 0.1-0.3 wt wt.% of V, 0.1-0.3 wt wt.% of Ta, 0.05-0.15 wt wt.% of C and the balance of Fe, and the mass of the added Sc 4Zr3O1 powder is 0.2-1.0 wt wt.% of Sc 4Zr3O1 powder based on the mass of the martensitic steel atomized powder.
Further, the material preparation method comprises the following steps:
S1, synthesizing Sc 4Zr3O12 oxide, namely mixing scandium nitrate hydrate and stearic acid to obtain a mixture A, mixing zirconium nitrate hydrate and stearic acid to obtain a mixture B, heating the mixture A to melt stearic acid and stirring to obtain a mixed solution C, heating the mixture B to melt stearic acid and stirring to obtain a mixed solution D, mixing the mixed solution C and the mixed solution D, dripping acid and alkali to enable the mixed solution to be in a milky white colloid state, drying colloid, calcining, grinding to enable the powder to be thinned to be below 200nm, and obtaining Sc 4Zr3O12 powder.
Preferably, scandium nitrate hydrate and stearic acid are respectively weighed according to the molar ratio of 1:8-1:15, a mixture A is obtained by mixing, zirconium nitrate hydrate and stearic acid are respectively weighed according to the molar ratio of 1:8-1:15, a mixture B is obtained by mixing, the mixture A is heated in a water bath until the stearic acid is melted and stirred to obtain a mixed solution C, the mixture B is heated in a water bath until the stearic acid is melted and stirred to obtain a mixed solution D, the mixed solution C and the mixed solution D are mixed and stirred, acid and alkali are dropwise added to enable the mixed solution to be in a milky colloid state, the colloid is dried to 10-18: h and then calcined in a muffle furnace at the calcining temperature of 800-1200 ℃, and the calcined white powder is ground to enable the powder to be thinned to be below 200 nm;
S2, powder alloying, namely manufacturing an electrode by using Chinese low-activation martensitic (CLAM) steel, enabling the end face of the CLAM steel to be in a molten state with an arc contact area through discharge, and throwing out metal liquid drops through high-speed rotating centrifugal force to finish the powder preparation process. Weighing the dried CLAM steel powder, wherein the CLAM steel powder comprises 8.5-9.5wt.% of Cr, 1-2 wt wt.% of W, 0.3-0.6 wt wt.% of Mn, 0.1-0.3 wt wt.% of V, 0.1-0.3 wt wt.% of Ta and 0.05-0.15 wt wt.% of C, adding 0.2-1.0 wt wt.% of Sc 4Zr3O12 powder into the dried CLAM steel powder, and performing ball milling together with grinding balls to obtain alloyed powder;
Preferably, the dried atomized powder and Sc 4Zr3O12 powder are weighed, and are filled into a stainless steel pot together with grinding balls, high-purity argon is filled after vacuumizing, ball milling is carried out after 3-5 times of repetition, the ball milling speed is 280-380 r/min, and alloying powder is obtained after ball milling is 36-72 h;
s3, spark plasma sintering, namely cold press molding and sintering the alloyed powder, cooling the alloyed powder to room temperature along with a furnace, taking out a sintered sample, and keeping a vacuum state in the sintering process;
Preferably, 10-20g of alloying powder is put into a graphite mould with the diameter of 20-30mm, cold-pressed and molded by a graphite paper bag, then put into sintering equipment, the sintering pressure is 55-70MPa, the heating rate is 60-100 ℃ per min, the temperature is raised to 1000-1070 ℃ and then kept for 5-8min, and a sintered sample is taken out after being cooled to room temperature along with a furnace;
s4, heat treatment, namely heating up the sintered sample, preserving heat, air-cooling to room temperature for normalizing, heating up the sample, preserving heat, and then air-cooling to room temperature for tempering.
Preferably, the common heat treatment process specifically comprises the steps of placing a sample into a muffle furnace, heating to a temperature of 8-15 ℃ per minute, preserving heat for 30-90min after heating to 1050 ℃, taking out the sample, air-cooling the sample to room temperature, placing the sample into the muffle furnace, preserving heat for 90-120min after heating to 750 ℃ at 8-15 ℃, and then air-cooling the sample to room temperature. Preferably, the ODS martensitic steel heat treatment process specifically comprises the steps of placing a sample into a muffle furnace, heating to a temperature of 8-15 ℃ per minute, preserving heat for 30-90min after heating to 1300 ℃, cooling to room temperature along with the furnace at 5 ℃ per minute, heating to 1050 ℃ at 8-15 ℃ per minute, preserving heat for 30-90min, then air-cooling to room temperature, heating to 750 ℃ at 8-15 ℃ per minute, preserving heat for 90-120min, and then air-cooling to room temperature.
Further, after the heat treatment, EBSD samples were prepared by electropolishing. The EBSD sample preparation method is described in the patent of the disclosure of the present subject group (CN 114894826 a), and is not described here.
The invention further provides a preparation method of the heat-resistant irradiation-resistant superfine grain martensitic steel, which is prepared by adopting the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, the preparation of heat-resistant and irradiation-resistant ultra-fine grain martensitic steel is realized, sc 4Zr3O12 oxide is used for replacing nano Y 2O3 phase added in the traditional ODS steel preparation, on one hand, irradiation-resistant amorphization of the nano phase is improved, because the delta-A 4B3O12 structure has good irradiation resistance, and on the other hand, the ultra-fine grain martensitic steel is obtained, and has good tensile property.
The invention is suitable for various iron-based high-temperature structural materials with superfine grains, can improve the heat resistance and irradiation resistance of the materials, and does not increase the preparation cost while improving the performance compared with the traditional ODS steel.
Drawings
FIG. 1 is an XRD pattern for the oxide of Sc 4Zr3O12 in example 1;
FIG. 2 is a secondary electron image of (a) 9Cr-ODS steel and (b) EBSD image in example 1;
FIG. 4 is an SEM image of 9Cr-ODS steel of example 2;
FIG. 5 is a secondary electron image of (a) 9Cr-ODS steel and (b) EBSD image in comparative example 1;
FIG. 6 is an SEM image of 9Cr-ODS steel of comparative example 2;
FIG. 3 is a graph showing the results of drawing at room temperature and at high temperature of (a) 9Cr-ODS steel in example 1 and comparative example 1.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and intended to be illustrative of the invention and not to be construed as limiting the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a preparation method of heat-resistant and radiation-resistant ultrafine grain martensitic ODS steel, wherein heat-resistant refers to stable high-temperature structure and good high-temperature strength of a material, radiation resistance is realized by adding radiation-resistant oxide, ultrafine grains refer to grains smaller than 1 mu m, the oxide dispersion strengthening (Oxide dispersion strengthened, ODS) steel is a conventional definition in the field, and the conventional ODS steel in the field is suitable for the preparation method of a sample in the field and is not specifically described herein.
The preparation method comprises the steps of preparing Sc 4Zr3O12 powder by a chemical synthesis method, replacing a nano Y 2O3 phase added in the preparation of traditional ODS steel, so as to improve the irradiation resistance of the nano phase, and comprises the following specific processes:
Scandium nitrate hydrate, stearic acid, zirconium nitrate hydrate and stearic acid are respectively weighed according to the molar ratio of 1:10, heated in a water bath at 90 ℃ for about 30min until the stearic acid is melted, magnetically stirred for about 120min to uniformly mix the mixed solution, scandium nitrate solution and zirconium nitrate solution which are dissolved into the stearic acid are magnetically stirred for 30min, acid and alkali are dripped to enable the mixed solution to be in a milky white colloid state, the colloid is baked for 10-18h and then calcined for 1-5h at 800-1200 ℃, and then ceramic ball milling is used for grinding the powder for 10-20h, so that the particle size of the powder is thinned to be below 200 nm.
Further, the mixed powder is ball-milled, and the dried matrix powder and the Sc 4Zr3O12 oxide powder are weighed. The mixed powder and grinding balls are put into a stainless steel pot, the diameters of the grinding balls are phi 10mm and phi 5mm respectively, the mass ratio is 1:5, the ball milling pot is vacuumized and filled with high-purity argon, the process is repeated for 3-5 times, the ball milling speed is 300r/min, and the alloyed powder is obtained after ball milling for 48 hours. This step is mainly aimed at increasing the degree of alloying of the powder, refining the oxide, and increasing the amount of dissolved oxide.
Further, the step of spark plasma sintering is carried out after ball milling. The specific process comprises the steps of heating to 1050 ℃ at a temperature of 100 ℃ per minute, preserving heat for 5min, cooling to room temperature, taking out a sintered sample, and keeping a vacuum state in the sintering process.
Preferably, in some embodiments of the present invention, the process of heat treatment is performed after ball milling and spark plasma sintering, and the fully martensitic structure may be obtained by a suitable heat treatment process. According to the embodiment of the invention, the heat treatment process comprises the steps of 1) cutting a test sample by using a wire cutting machine, placing the test sample into a muffle furnace, heating to 10 ℃ per minute, preserving heat for 60 minutes after heating to 1050 ℃, taking out the sample, cooling the sample to room temperature by air, placing the sample into the muffle furnace, heating to 750 ℃ per minute, preserving heat for 120 minutes, and cooling the sample to room temperature by air, and 2) placing the sample into a tube furnace, heating to 10 ℃ per minute, heating to 1300 ℃ and preserving heat for 60 minutes, cooling to room temperature by 5 ℃ per minute along with the furnace, heating to 1050 ℃ per minute, preserving heat for 60 minutes, cooling to room temperature by air, heating to 750 ℃ per minute, preserving heat for 120 minutes, and cooling to room temperature by air. The first heat treatment scheme was only normalizing and tempering, and was suitable for the ODS steel in example 1, but not for the conventional ODS, as described in comparative example 1. The second heat treatment scheme adds one-step high-temperature heat treatment, overcomes the pinning effect of nano particles at high temperature, directly converts residual ferrite grains which are not austenitized into delta-ferrite, obtains uniform austenite structure through austenitization, and obtains martensite structure through cooling. The second scheme enables the conventional ODS steel to obtain a martensitic structure as in comparative example 2.
The present invention is illustrated by the following specific examples, which are given for illustrative purposes only and are not intended to limit the scope of the present invention in any way. Unless otherwise specified, the conditions or procedures are not specifically described and the reagents used are all commercially available.
The absolute ethyl alcohol, ammonia water, scandium nitrate hydrate, zirconium nitrate hydrate, stearic acid, billion of oxide and titanium powder adopted in the embodiment of the invention are all commercially available analytical pure reagents.
The equipment adopted for calcination in the embodiment of the invention is a GSL-1200X type muffle furnace.
The model of the spark plasma sintering equipment is SE-607-FCZ type.
The XRD diffractometer device model of the embodiment of the invention is X' Pert Powder PANALYTICAL.
In the embodiment of the invention, SEM equipment adopted for observing the appearance of the sample is Sigma IGMA of ZEISS company in Germany, and the equipment is provided with an electron back scattering diffraction probe (Electron Back Scattered Diffraction, EBSD; equipment model number is NORDLYS).
Example 1
The components (mass fraction) of the heat-resistant and irradiation-resistant ultra-fine grain martensitic steel in the embodiment are Fe-9Cr-1.5W-0.4Mn-0.15Ta-0.2V-0.1C-0.5 Sc 4Zr3O12, and the preparation steps of the sample are as follows:
s1, oxide synthesis, namely respectively weighing scandium nitrate hydrate and stearic acid, zirconium nitrate hydrate and stearic acid according to a molar ratio of 1:10, wherein the molar ratio of scandium to zirconium is 4:3, heating in a 90 ℃ water bath for about 30min until the stearic acid is melted, magnetically stirring for 120min until the mixed solution is uniform, mixing scandium nitrate solution dissolved with the stearic acid with zirconium nitrate solution, magnetically stirring for 30min, dropwise adding diluted ammonia water until the solution PH is 6.5 at a dropping speed of 1-5mL/min, enabling the mixed solution to be in a milky colloid state, drying the colloid for 12h, calcining the colloid in a muffle furnace for 4h at 1000 ℃, and grinding calcined white powder for 10h to refine the powder to below 200 nm;
S2, powder alloying, namely manufacturing an electrode by using Chinese low-activation martensitic (CLAM) steel, enabling the end face of the CLAM steel to be in a molten state with an arc contact area through discharge, and throwing out metal liquid drops through high-speed rotating centrifugal force to finish the powder preparation process. The components of the CLAM steel powder are Cr 8.68 wt percent, W1.43 wt percent, mn 0.31 wt percent, V0.23 wt percent, ta 0.21 wt percent, C0.13 wt percent and the balance Fe, the average grain diameter is 69 mu m, 89.55g of low-activation steel atomized powder and 0.45g of Sc 4Zr3O12 powder after weighing and drying are filled into a stainless steel pot together with 900g of grinding balls, high-purity argon is filled after vacuumizing, ball milling is carried out after 3-5 times, the ball milling speed is 300r/min, and alloying powder is obtained after ball milling is carried out for 48 hours;
S3, spark plasma sintering, namely wrapping 20g of alloyed powder with graphite paper, cold-pressing and molding, then loading the powder into sintering equipment, heating to 100 ℃ per min, heating to 1050 ℃, preserving heat for 5min, cooling to room temperature along with a furnace, taking out a sintered sample, and keeping a vacuum state in the sintering process;
S4, heat treatment, namely grinding graphite paper on the surface of the sintered sample, cutting the test sample by using a wire cutting machine, placing the test sample into a muffle furnace, heating to the temperature of 1050 ℃ at the temperature of 10 ℃ per min, preserving heat for 60min, taking out the sample, air-cooling the sample to the room temperature, placing the sample into the muffle furnace, heating to the temperature of 750 ℃ at the temperature of 10 ℃ per min, preserving heat for 120min, and then air-cooling the sample to the room temperature.
FIG. 1 shows XRD patterns of the oxide of Sc 4Zr3O12 in example 1, and FIG. 2 shows secondary electron images of (a) 9Cr-ODS steel and (b) EBSD patterns in example 1. XRD test shows that the single phase Sc 4Zr3O12 powder with excellent crystallinity is obtained, and EBSD is used for tissue characterization of the sample, and the result shows that the martensitic ODS steel with superfine grains is obtained, the average grain size is 0.92 mu m, the grain size is uniform, and no obvious bimodal distribution is seen. The room temperature tensile strength of the material reaches 1075MPa, the elongation rate reaches 18 percent, and the strength reaches approximately 300MPa at a high temperature of 650 ℃ (as shown in figure 3).
Example 2
The components of the heat-resistant and irradiation-resistant martensitic steel in the comparative example are Fe-9Cr-1.5W-0.4Mn-0.15Ta-0.2V-0.1C-0.5 Sc 4Zr3O12, and the preparation steps of the sample are as follows:
s1, synthesizing an oxide, wherein the method is the same as that in the embodiment 1;
S2, powder alloying, wherein the same example 1 is adopted;
s3, spark plasma sintering, wherein the same example 1 is adopted;
S4, heat treatment, namely placing the sample into a tube furnace, wherein the temperature rising speed is 10 ℃ per minute, heating to 1300 ℃ and preserving heat for 60 minutes, cooling to room temperature along with the furnace at 5 ℃ per minute, heating to 1050 ℃ at 10 ℃ per minute, preserving heat for 60 minutes, then air-cooling to room temperature, heating to 750 ℃ at 10 ℃ per minute, preserving heat for 120 minutes, and then air-cooling to room temperature.
FIG. 4 is a SEM image of 9Cr-ODS steel of example 2, and the test sample was also able to obtain a martensitic structure under a high temperature heat treatment process by scanning electron microscopy, and the austenitic grain size of the sample was not more than 10 μm, which is similar to that of the conventional martensitic steel, but coarser than that of the sample of example 1.
Comparative example 1
The components of the heat-resistant and radiation-resistant martensitic steel in the comparative example are Fe-9Cr-1.5W-0.4Mn-0.15Ta-0.2V-0.1C-0.13Ti-0.3Y 2O3, and the sample preparation steps are as follows:
s1, powder alloying, wherein the same example 1 is used, but 0.12g of Ti powder, 0.27g Y 2O3 g of powder and 89.63g of atomized powder are weighed and dried;
s2, spark plasma sintering, wherein the method is the same as that of the embodiment 1;
S3, heat treatment, wherein the same as in the embodiment 1.
FIG. 5 is a secondary electron image of (a) 9Cr-ODS steel and (b) EBSD of comparative example 1, which were characterized by the sample structure using EBSD, and it was shown that the average grain size of the ODS steel of comparative example 1 was 0.9 μm, which is similar to that of example 1, but the grain distribution was not uniform, and that ultrafine grains having a size of less than 500nm and coarse grains having a size of more than 7 μm were present, and that a large number of polygonal ferrite grains were present. The tensile strength of the material at room temperature is 1012MPa, and the tensile strength at high temperature is 244MPa at 650 ℃. The room temperature strength was similar to that of example 1, but the high temperature strength was reduced by 20%.
Comparative example 2
The components of the heat-resistant and radiation-resistant martensitic steel in the comparative example are Fe-9Cr-1.5W-0.4Mn-0.15Ta-0.2V-0.1C-0.13Ti-0.3Y 2O3, and the sample preparation steps are as follows:
S1, powder alloying, wherein the same comparison example 1 is adopted;
s2, spark plasma sintering, wherein the method is the same as that of the embodiment 1;
s3, heat treatment, wherein the same as in the embodiment 2.
FIG. 6 is an SEM image of 9Cr-ODS steel of comparative example 2, and the sample of ODS steel of comparative example 2 was subjected to the same heat treatment process as in example 2, and a martensitic structure was obtained, but the austenitic grain size of the sample was larger than that of example 2, exceeding 10. Mu.m.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity, however, they should be considered as the scope of coverage of this specification as long as there is no contradiction between the combinations of the technical features. Accordingly, the scope of the invention should be assessed as that of the appended claims.
Claims (5)
1. A preparation method of heat-resistant and irradiation-resistant superfine grain martensitic steel is characterized in that atomized spherical powder and Sc 4Zr3O12 oxide powder are mixed, and ball milling, spark plasma sintering and heat treatment are carried out to prepare a material;
The atomized spherical powder is prepared by manufacturing an electrode by using Chinese low-activation martensitic (CLAM) steel, enabling the end face of the CLAM steel to be in a molten state in an arc contact area through discharge, throwing out metal liquid drops through rotary centrifugal force to finish the powder preparation process, and screening out powder with the particle size of 200-300 meshes, wherein the powder comprises, by mass, 8.5-9.5% of Cr, 1-2 wt% of W, 0.3-0.6 wt% of Mn, 0.1-0.3 wt% of V, 0.1-0.3 wt% of Ta, 0.05-0.15 wt% of C and the balance Fe;
The mass ratio of Sc 4Zr3O12 oxide powder to atomized spherical powder is 1:500-1:100, the heat treatment is a common heat treatment process or an ODS martensitic steel heat treatment process, the common heat treatment process comprises the steps of placing a sample obtained after sintering into a muffle furnace, heating to 1050 ℃ at a heating rate of 10-15 ℃ per minute, preserving heat for 30-90min, taking out the sample, air-cooling to room temperature, placing the sample into the muffle furnace, heating to 750 ℃ at a heating rate of 8-15 ℃ per minute, preserving heat for 90-120min, and then air-cooling to room temperature, wherein the sample obtained after sintering is placed into the muffle furnace, heating to 1300 ℃ at a heating rate of 10-15 ℃ per minute, preserving heat for 30-90min, cooling to room temperature along with the furnace at a cooling rate of 5 ℃ per minute, heating to 1050 ℃ at a heating rate of 8-15 ℃ per minute, preserving heat for 30-90min, then air-cooling to room temperature, placing the sample into the muffle furnace, heating to room temperature at a heating rate of 8-15 ℃ per minute, and preserving heat for the rest of the superfine Fe crystal grain component of which is air-cooled to room temperature of the rest of the steel, heating to ：Cr 8.5-9.5 wt.％,W 1-2 wt.％,Mn 0.3-0.6wt.％,V 0.1-0.3 wt.％,Ta 0.1-0.3 wt.％,C 0.05-0.15 wt.％,Sc4Zr3O12：0.2-1.0wt.%, ℃ at a temperature of 20 ℃ at a temperature of the temperature of 20 ℃ after sintering.
2. A method for preparing heat-resistant irradiation-resistant ultra-fine grain martensitic steel according to claim 1, characterized in that Sc 4Zr3O12 oxide powder is prepared by synthesis using a gel sol method.
3. The method for preparing the heat-resistant and irradiation-resistant ultrafine grain martensitic steel is characterized in that the ball milling process comprises the steps of grinding Sc 4Zr3O12 oxide powder by using a ceramic pot, wherein the mass ratio of ceramic balls to powder is 20:1, the volume of alcohol is 2/3 of that of the ceramic pot, the autorotation speed of the ball milling pot is 200-300 r/min, and the grinding time is 10-20h.
4. The method for preparing the heat-resistant and irradiation-resistant ultrafine grain martensitic steel is characterized in that the ball milling comprises the steps of mechanically alloying Sc 4Zr3O12 powder and atomized spherical powder, wherein the mass ratio of the spherical materials is 10:1-15:1, the autorotation speed of a ball milling tank is 280-380 r/min, and the milling time is 36-72h.
5. The method for preparing heat-resistant irradiation-resistant ultra-fine grain martensitic steel according to claim 1, wherein the spark plasma sintering process comprises the steps of loading alloy powder obtained by ball milling into a graphite mold, heating to 1000-1070 ℃ at a heating rate of 60-100 ℃ per minute, preserving heat for 5-8 min, cooling to room temperature along with a furnace, and taking out for later use.
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