CN111809119A - Dispersion strengthening FeCrAl alloy material - Google Patents
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- CN111809119A CN111809119A CN202010697164.XA CN202010697164A CN111809119A CN 111809119 A CN111809119 A CN 111809119A CN 202010697164 A CN202010697164 A CN 202010697164A CN 111809119 A CN111809119 A CN 111809119A
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
The invention discloses a dispersion strengthening FeCrAl alloy material, which is a nano ZrC dispersion FeCrAl alloy material; according to weight percentage, the Cr content is 10-16%, the Al content is 3-6%, the Mo content is 0.1-3%, the Nb content is 0.01-2%, the ZrC nano-particles content is 0.2-3.0%, and the balance is iron and impurities meeting the industrial standard. The invention obtains the cladding material of the nano ZrC dispersed FeCrAl alloy for the nuclear reactor by selecting the nano ZrC dispersed FeCrAl alloy and optimizing the contents of alloy elements and nano reinforcing phases, so that the FeCrAl-based alloy has higher high-temperature strength and high-temperature stability, and simultaneously has good room-temperature mechanical property and plasticity suitable for processing.
Description
Technical Field
The invention relates to the technical field of iron-based structural materials and special alloy materials, in particular to a dispersion-strengthened FeCrAl alloy material which is used for a reactor core structural material and a fuel element cladding material in a pressurized water reactor.
Background
After the Japanese Fudao nuclear accident, the cladding material for the nuclear reactor is required to have better high-temperature steam oxidation resistance and provide larger safety margin to avoid the potential core melting accident compared with the existing zirconium alloy cladding. Research shows that the FeCrAl-based alloy containing proper Cr and Al contents is a promising candidate material in the cladding material of the advanced nuclear reactor (such as military nuclear power reactor) because of excellent high-temperature steam oxidation resistance, good irradiation resistance, corrosion resistance and the like.
The FeCrAl alloy containing proper Cr and Al contents is used as the reactor cladding material, and in addition to meeting the performance requirements, the FeCrAl alloy also has the following properties:
1. the alloy has higher strength and plasticity at room temperature, and provides a foundation for processing thin-wall clad pipes;
2. the alloy has higher strength at high temperature (not lower than 800 ℃), and provides a foundation for reliability under high-temperature working conditions;
3. the alloy has stable high-temperature structure, stronger structure thermal stability and stable and unchanged grain size at the temperature of over 800 ℃ for a longer time.
In the existing FeCrAl alloy material, the material which can meet the performance requirements and can meet the requirements for reactor core structures such as fuel element cladding, framework and the like is not available.
Disclosure of Invention
Aiming at the technical problems, the invention provides a dispersion strengthening FeCrAl alloy material for solving the problems, so that the FeCrAl-based alloy has higher high-temperature strength and high-temperature stability, and simultaneously has good room-temperature mechanical properties and plasticity suitable for processing.
The invention is realized by the following technical scheme:
a dispersion strengthening FeCrAl alloy material is a nano ZrC dispersion FeCrAl alloy material; according to weight percentage, the Cr content is 10-16%, the Al content is 3-6%, the Mo content is 0.1-3%, the Nb content is 0.01-2%, the ZrC nano-particles content is 0.2-3.0%, and the balance is iron and impurities meeting the industrial standard.
At present, FeCrAl alloy containing proper Cr and Al contents is used as a reactor cladding material, and generally meets the requirements of high-temperature steam oxidation resistance, good irradiation resistance, corrosion resistance and the like, but cannot simultaneously have the following properties: the alloy has higher strength and plasticity at room temperature; the alloy has higher strength at high temperature (not lower than 800 ℃), and provides a foundation for reliability under high-temperature working conditions; the alloy has stable high-temperature structure, stronger structure thermal stability and stable and unchanged grain size at the temperature of over 800 ℃ for a longer time.
Based on the technical background, the invention aims to obtain the nano ZrC dispersed FeCrAl alloy cladding material for the nuclear reactor by selecting the nano ZrC dispersed FeCrAl alloy and optimizing the contents of alloy elements and nano reinforcing phases. In the alloy, the ZrC particles have the advantages of high melting point, high hardness, low neutron absorption cross section and the like, the nanometer ZrC particles can effectively pin dislocation and grain boundary movement, inhibit grain growth under a high-temperature condition, remarkably improve the high-temperature strength and the structural stability of the FeCrAl-based alloy, and are beneficial to improving the capability of the FeCrAl-based alloy in resisting serious accidents; meanwhile, the neutron absorption section of ZrC is more than that of other types of reinforcing phases such as TiC and HfC、Y2O3、La2O3And the like is lower, which is beneficial to improving the neutron economy of FeCrAl-based alloy. In addition, a large amount of phase interfaces existing between the ZrC particles with the nanometer size and the alloy matrix are also beneficial to absorbing point defects generated by irradiation, thereby being beneficial to improvingHigh radiation resistance of the alloy. The FeCrAl-based alloy provided by the invention has higher high-temperature strength and structural stability, and simultaneously has good room-temperature mechanical properties and plasticity suitable for processing.
More preferably, the steel comprises, by weight, 10% -16% of Cr, 3% -6% of Al, 1.5% -3% of Mo, 0.5% -2% of Nb, 0.3% -2% of ZrC, and the balance of iron and impurities meeting industrial standards.
More preferably, the total content of Cr and Al is more than or equal to 16.5%.
More preferably, the steel comprises, by weight, 13.2% of Cr, 5.6% of Al, 0.1% of Mo, 0.1% of Nb, 0.3-2% of ZrC, and the balance of Fe and impurities meeting industrial standards.
More preferably, in the impurities meeting the industrial standard, O is less than or equal to 0.02 percent, and N is less than or equal to 0.005 percent.
For the FeCrAl alloy, as a Fe-based alloy, other elements are auxiliary addition elements, the addition types of the elements, the addition amount of the elements and the addition amount of each element have important influence on the performance of the FeCrAl alloy, and the interaction/reaction characteristics of different trace elements and the influence rules of the interaction/reaction characteristics on the performance of the zirconium alloy are different. The invention further optimizes and designs the addition of each element, and is beneficial to obtaining FeCrAl alloy with better mechanical property and high-temperature stability.
Further preferably, the average size of the ZrC nanoparticles is 3nm to 100 nm.
Further preferably, the average size of the ZrC nanoparticles is 3nm to 60 nm.
Further preferably, the average size of the ZrC nanoparticles is 3nm to 20 nm.
ZrC is used as a nano disperse phase, the average size of the ZrC has important influence on the mechanical property and the structure stability of the alloy, the smaller the particles are, the smaller the size is, the better the mechanical property of the FeCrAl alloy is, and the more stable the structure is.
The application of the dispersion strengthening FeCrAl alloy material is used as an alloy material for a reactor. Further preferably, the alloy material for a reactor includes a core structure material and a fuel element cladding material.
According to the invention, the nano-sized ZrC particles are added into the FeCrAl-based alloy, so that the crystal grains can be obviously refined, the high-temperature strength and the structural stability of the FeCrAl-based alloy are improved, and the FeCrAl-based alloy has good room-temperature mechanical properties and plasticity suitable for processing. The nano ZrC reinforced FeCrAl alloy material has remarkable mechanical property and good high-temperature thermal stability, and can be used as a material of reactor core structures such as fuel element cladding, framework and the like in a nuclear power reactor.
The invention has the following advantages and beneficial effects:
1. the invention obtains the nano ZrC dispersed FeCrAl alloy cladding material for the nuclear reactor by selecting the nano ZrC dispersed FeCrAl alloy and optimizing the contents of alloy elements and nano reinforcing phase. By adding the nano-sized ZrC particles into the FeCrAl-based alloy, the crystal grains can be obviously refined, the high-temperature strength and the structural stability of the FeCrAl-based alloy are improved, and the FeCrAl-based alloy has good room-temperature mechanical properties and plasticity suitable for processing.
2. The invention provides a nano ZrC reinforced FeCrAl-based alloy structural material with a relatively stable structure at high temperature (not lower than 800 ℃), wherein after annealing at 1000 ℃ for 5 hours, the grain size is relatively stable, and the average grain size is about 1 mu m; in addition, the nano ZrC reinforced fine-grain FeCrAl-based alloy material has very obvious high-temperature strength, the tensile strength of the alloy at 800 ℃ reaches more than 110MPa, and the tensile strength is improved by about 3 times compared with that of the common FeCrAl alloy; the nanometer ZrC reinforced fine grain FeCrAl alloy material has remarkable mechanical property and good high-temperature thermal stability, and can be used as a material of reactor core structures such as fuel element cladding, framework and the like in a nuclear power reactor.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is an electron backscatter diffraction pattern; in the drawings, fig. 1(a) shows an electron backscatter diffraction pattern of the alloy material of comparative example 1, fig. 1(b) shows an electron backscatter diffraction pattern of the alloy material of example 2, and fig. 1(c) shows an electron backscatter diffraction pattern of the alloy material of example 3.
FIG. 2 is a transmission electron microscope photograph showing the results of example 2 of the present invention.
FIG. 3 is a drawing graph; in which fig. 3(a) shows the room temperature tensile curve of the alloy materials of comparative example 1 and example 2, and fig. 3(b) shows the high temperature tensile curve of the alloy materials of comparative example 1 and example 2.
FIG. 4 is a room temperature tensile curve before and after annealing at 1000 ℃ for 5 hours; in the figure 4(a) shows the room temperature tensile curve before and after annealing at 1000 ℃ for 5h in comparative example 1, and figure 4(b) shows the room temperature tensile curve before and after annealing at 1000 ℃ for 5h in example 2.
FIG. 5 is an electron backscatter diffraction pattern, wherein FIG. 5(a) shows the electron backscatter diffraction pattern of comparative example 1 after annealing at 1000 ℃ for 5 hours, and FIG. 5(b) shows the electron backscatter diffraction pattern of example 2 after annealing at 1000 ℃ for 5 hours.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1
This example provides a nanometer ZrC dispersion strengthening FeCrAl alloy material, adopts FeCrAl pre-alloyed powder and ZrC powder as raw materials. According to the weight percentage, the content of Cr in FeCrAl pre-alloy powder is 13.2 percent, the content of Al is 5.6 percent, the content of Mo is 0.1 percent, the content of Nb is 0.1 percent, and the balance is iron and impurities meeting the industrial standard. The average size of ZrC powder particles is 30-40 nm.
Weighing FeCrAl pre-alloy powder and ZrC powder according to the mass ratio of 99.5:0.5, and performing ball-milling mixing, sintering, forging and other processes to obtain the FeCrAl-based alloy.
Example 2
This example provides a nanometer ZrC dispersion strengthening FeCrAl alloy material, adopts FeCrAl pre-alloyed powder and ZrC powder as raw materials. According to the weight percentage, the content of Cr in FeCrAl pre-alloy powder is 13.2 percent, the content of Al is 5.6 percent, the content of Mo is 0.1 percent, the content of Nb is 0.1 percent, and the balance is iron and impurities meeting the industrial standard. The average size of ZrC powder particles is 30-40 nm.
Weighing FeCrAl pre-alloy powder and ZrC powder according to a mass ratio of 99:1, and performing ball-milling mixing, sintering, forging and other processes to obtain the FeCrAl-based alloy.
Example 3
This example provides a nanometer ZrC dispersion strengthening FeCrAl alloy material, adopts FeCrAl pre-alloyed powder and ZrC powder as raw materials. According to the weight percentage, the content of Cr in FeCrAl pre-alloy powder is 13.2 percent, the content of Al is 5.6 percent, the content of Mo is 0.1 percent, the content of Nb is 0.1 percent, and the balance is iron and impurities meeting the industrial standard. The average size of ZrC powder particles is 30-40 nm.
Weighing FeCrAl pre-alloy powder and ZrC powder according to a mass ratio of 98:2, and performing ball-milling mixing, sintering, forging and other processes to obtain the FeCrAl-based alloy.
Example 4:
this example provides a nanometer ZrC dispersion strengthening FeCrAl alloy material, adopts FeCrAl pre-alloyed powder and ZrC powder as raw materials. According to the weight percentage, the content of Cr in FeCrAl pre-alloy powder is 10 percent, the content of Al is 6 percent, the content of Mo is 3 percent, the content of Nb is 2 percent, and the balance is iron and impurities meeting the industrial standard. The average size of ZrC powder particles is 30-40 nm.
Comparative example 1
The comparative example provides a FeCrAl alloy material, the same as the scheme of example 2, with the following differences: no ZrC was added.
The performance characterization analysis is as follows:
1. characterization and analysis of grain structure morphology of FeCrAl-based alloy
The grain structure morphology of the FeCrAl-based alloys of examples 2-3 and comparative example was analyzed by an electron back-scattering diffractometer, and the test results are shown in FIG. 1: the average grain sizes of example 2 (shown in FIG. 1 (b)) and example 3 (shown in FIG. 1 (c)) were measured to be 0.8 μm and 0.7 μm, respectively, while the average grain size of the comparative example FeCrAl-based alloy (shown in FIG. 1 (a)) was 1.5 μm, indicating that the addition of nanosized ZrC particles was effective in suppressing the alloy grain growth.
2. Characterization and analysis of distribution condition of nano ZrC particles in FeCrAl-based alloy
The invention takes example 2 as an example, and the distribution of nano-ZrC particles in FeCrAl-based alloy of example 2 is characterized by using a transmission electron microscope, and the result is shown in FIG. 2: ZrC particles in the FeCrAl-based alloy are fine and uniformly distributed, and the fine and dispersedly distributed ZrC particles can effectively block dislocation and movement of crystal boundary, so that the strength and high-temperature stability of the FeCrAl-based alloy are improved.
3. Mechanical Property test
(1) Test object
Examples 1-3 and comparative example 1.
(2) Test method and conditions
The FeCrAl-based alloys of examples 1-3 and comparative example 1 were subjected to room temperature tensile and high temperature tensile tests using a universal material testing machine, and hardness tests using a micro Vickers hardness tester.
Wherein, the high-temperature tensile strength test is to test the mechanical property at 800 ℃.
(4) Test results
The results of the room temperature tensile strength, room temperature elongation, high temperature tensile strength and hardness measurements are shown in Table 1:
table 1 mechanical property test results of FeCrAl-based alloy materials provided in examples 1-3 and comparative example 1
As shown in Table 1, under the condition of room temperature, the room-temperature tensile strength distribution of the examples 1-3 is 793MPa, 844MPa and 862MPa, the strength is remarkably higher than 757MPa of the comparative example, meanwhile, the examples 1-2 also have good room-temperature plasticity, and the plasticity of the examples 1-3 meets the requirement of conventional processing; at 800 ℃, the tensile strengths of examples 1-3 are 76MPa, 92MPa and 114MPa respectively, which are obviously higher than 55MPa of the FeCrAl-based alloy in the comparative example; the hardness of the examples 1-3 is higher than that of the comparative example, which shows that the FeCrAl-based alloy provided by the invention has excellent room-temperature and high-temperature strength and hardness. Among them, example 2 has high strength, excellent plasticity, and excellent comprehensive mechanical properties.
4. High temperature stability test
(1) Test object
Examples 1-3 and comparative example 1.
(2) Test method and conditions
Annealing the example 2 and the comparative example 1 at 1000 ℃ for 5h, and performing high-temperature annealing and heat preservation by adopting a common high-temperature box furnace; then, a universal material testing machine is adopted to carry out mechanical property test, and the mechanical property test method is the same as the above; and observing the grain structure morphology of the alloy by adopting an electron back scattering diffractometer.
(3) Test results
The mechanical property test result is shown in fig. 4, according to the mechanical property test result of fig. 4, after annealing at 1000 ℃ for 5 hours, the room temperature plastic change of the comparative example and the example 2 is not large, but the room temperature tensile strength of the comparative example is reduced to 560MPa from 757MPa before annealing, while the tensile strength change of the example 2 is small and is only reduced to 828MPa from 844MPa before annealing, which shows that the FeCrAl base alloy provided by the invention has excellent high temperature stability and can keep good mechanical property after high temperature annealing.
The morphology of the grain structure of the alloy was observed using an electron back-scattering diffractometer, and the results are shown in fig. 5. According to the results of the microstructure analysis of fig. 5, the grain size of example 2 is relatively stable after annealing at 1000 ℃ for 5h, with an average grain size around 1 μm, whereas the average grain size of the comparative example FeCrAl-based alloy grows from 1.5 μm to nearly one hundred microns, indicating that the FeCrAl-based alloy of the present invention has a very good structural stability at high temperatures.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A dispersion strengthening FeCrAl alloy material is characterized in that a nano ZrC dispersion FeCrAl alloy material is used; according to weight percentage, the Cr content is 10-16%, the Al content is 3-6%, the Mo content is 0.1-3%, the Nb content is 0.01-2%, the ZrC nano-particles content is 0.2-3.0%, and the balance is iron and impurities meeting the industrial standard.
2. The dispersion-strengthened FeCrAl alloy material as claimed in claim 1, wherein the dispersion-strengthened FeCrAl alloy material comprises, in weight percent, 10% to 16% of Cr, 3% to 6% of Al, 1.5% to 3% of Mo, 0.5% to 2% of Nb, 0.3% to 2% of ZrC, and the balance of Fe and impurities meeting industrial standards.
3. The dispersion-strengthened FeCrAl alloy material as claimed in claim 1 or 2, wherein the total content of Cr and Al is not less than 16.5%.
4. The dispersion strengthened FeCrAl alloy material as claimed in claim 1, wherein the dispersion strengthened FeCrAl alloy material comprises, in weight percent, 13.2% Cr, 5.6% Al, 0.1% Mo, 0.1% Nb, 0.3-2% ZrC, and the balance iron and impurities meeting industry standards.
5. The dispersion-strengthened FeCrAl alloy material as claimed in claim 1, wherein the impurities meeting the industrial standards are O0.02% or less and N0.005% or less.
6. The dispersion strengthened FeCrAl alloy material as claimed in claim 1, wherein the ZrC nanoparticles have an average size of 3nm to 100 nm.
7. The dispersion strengthened FeCrAl alloy material as claimed in claim 6, wherein the ZrC nanoparticles have an average size of 3nm to 60 nm.
8. The dispersion strengthened FeCrAl alloy material as claimed in claim 7, wherein the ZrC nanoparticles have an average size of 3nm to 20 nm.
9. Use of a dispersion strengthened FeCrAl alloy material according to any of claims 1 to 7 as an alloy material for reactors.
10. The use of a dispersion strengthened FeCrAl alloy material according to claim 9, wherein the reactor alloy material comprises core structure material and fuel element cladding material.
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CN115852230A (en) * | 2022-09-09 | 2023-03-28 | 中国核动力研究设计院 | ZrC enhanced FeCrAl alloy and preparation method thereof |
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CN117778894A (en) * | 2024-02-01 | 2024-03-29 | 扬州三劦紧固件有限公司 | Heat-resistant high-strength fastener material and preparation system thereof |
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Cited By (10)
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CN113278895A (en) * | 2021-05-06 | 2021-08-20 | 中国科学院合肥物质科学研究院 | High-strength FeCrAl-based alloy |
CN114214568A (en) * | 2021-12-22 | 2022-03-22 | 中国核动力研究设计院 | High-strength heat-resistant dispersion-reinforced FeCrAl alloy material, and preparation method and application thereof |
CN114214568B (en) * | 2021-12-22 | 2022-10-14 | 中国核动力研究设计院 | High-strength heat-resistant dispersion-reinforced FeCrAl alloy material, and preparation method and application thereof |
CN114951691A (en) * | 2022-03-28 | 2022-08-30 | 上海大学 | Laser additive manufacturing method of ZrC particle reinforced FeCrAl metal matrix composite material for nuclear fuel cladding |
CN115852230A (en) * | 2022-09-09 | 2023-03-28 | 中国核动力研究设计院 | ZrC enhanced FeCrAl alloy and preparation method thereof |
CN115852230B (en) * | 2022-09-09 | 2024-03-19 | 中国核动力研究设计院 | ZrC reinforced FeCrAl alloy and preparation method thereof |
CN115896589A (en) * | 2022-11-04 | 2023-04-04 | 苏州热工研究院有限公司 | Oxide dispersion strengthening FeCrAl alloy and preparation method and application thereof |
CN115896589B (en) * | 2022-11-04 | 2024-04-05 | 苏州热工研究院有限公司 | Oxide dispersion strengthening FeCrAl alloy and preparation method and application thereof |
CN117778894A (en) * | 2024-02-01 | 2024-03-29 | 扬州三劦紧固件有限公司 | Heat-resistant high-strength fastener material and preparation system thereof |
CN117778894B (en) * | 2024-02-01 | 2024-09-13 | 扬州三劦紧固件有限公司 | Heat-resistant high-strength fastener material and preparation system thereof |
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