WO2020214057A1 - Радиационно-стойкая аустенитная сталь для внутрикорпусной выгородки ввэр - Google Patents
Радиационно-стойкая аустенитная сталь для внутрикорпусной выгородки ввэр Download PDFInfo
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- WO2020214057A1 WO2020214057A1 PCT/RU2019/001051 RU2019001051W WO2020214057A1 WO 2020214057 A1 WO2020214057 A1 WO 2020214057A1 RU 2019001051 W RU2019001051 W RU 2019001051W WO 2020214057 A1 WO2020214057 A1 WO 2020214057A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
-
- 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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- 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
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- 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
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
-
- 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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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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
- C21D2211/001—Austenite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Definitions
- the invention relates to the metallurgy of alloy steels and alloys, which are intended for use in nuclear power engineering in the production of the main equipment of nuclear power plants that meet the requirements of the safe operation of nuclear power, namely for the manufacture of in-vessel baffle water-cooled power reactors (VVER) with a resource of at least 60- years old.
- VVER in-vessel baffle water-cooled power reactors
- the baffle of the VVER reactor vessel is exposed to high-dose neutron irradiation and is operated in the water medium of the primary coolant, which is a corrosive medium [5].
- High-dose irradiation causes additional heating of the inner layers of the baffle and, as a consequence, their radiation swelling. Temperature gradients and swelling along the thickness of the baffle lead to the appearance of high tensile stresses in the surface layers of the baffle in contact with the aqueous medium. Contact of highly irradiated metal with the medium can lead to stress corrosion cracking of the baffle.
- the main negative factor of radiation swelling is the deformation of the baffle caused by it, which can lead to contact of the inner surface of the baffle with the peripheral fuel assemblies (FA) and, as a consequence, to the difficulty of removing fuel assemblies from the core.
- FA peripheral fuel assemblies
- This grade is characterized by insufficient resistance to radiation swelling according to the criterion of shape change and embrittlement at damaging doses, typical for the III + generation VVER inner baffle.
- the problem to be solved by the present invention is the creation of steel, which allows increasing the service life of VVER TOI internal parts (baffles) up to 60 years.
- the technical result of the present invention is the creation of an austenitic chromium-nickel steel with increased resistance to swelling when exposed to neutron fluxes at doses up to 150 dpa (displacements per atom), which provides a reduction in the shape change of the inner baffle during operation, as well as higher characteristics of plasticity and crack resistance in irradiated neutrons condition while maintaining resistance to stress corrosion cracking (compared to steel 08X18H10T).
- Such a set of properties of the new steel ensures the operability of the VVER TOI inner baffle during the design service life of at least 60 years.
- Chromium equivalent calculated by the formula:
- ⁇ DD ⁇ is the chromium content, wt. %; Cm about - the content of molybdenum, mass. %; Csi — silicon content, wt%; Cn - titanium content, wt. %.
- Cm is the nickel content, wt. %; ⁇ tone - carbon content, wt. %; CMP - manganese content, wt%; CN - nitrogen content, wt. %.
- the width of the selected ranges of the content of alloying elements is due to the metallurgical features of casting large ingots.
- the claimed invention is illustrated by the following graphic materials.
- Figure 1 shows the dependence of radiation swelling on the damaging dose for the prototype (forged metal JVfel) and the claimed steel with 20% nickel (forged metal No. 2).
- FIG. 2 shows the dependence of the radiation swelling on the damaging dose for the prototype (forged metal JNbl) and metal forgings N ° 3 H N ° 4.
- FIG. 3 shows a comparison of the deformation diagrams of the metal for forging N «3 (without REM and calcium) and forging N ° 4 (with REM and calcium) at forging temperatures.
- Table 1 contains data on the chemical composition of materials for forging No. 2 of the claimed steel grade and forging No. 1 of the prototype.
- Table 2 contains data on the chemical composition of materials for forgings .Nb 3 and No. 4 of the claimed steel grade.
- Table 3 reflects data on the mechanical properties of the claimed steel grade and prototype after austenitization at a temperature of 1050 ° C with cooling in water.
- the proposed steel like the prototype, is alloyed with carbon and titanium.
- the lower limit of the carbon content (0.06%) is regulated and the upper limit of the carbon content is increased to 0.1%.
- Alloying with titanium is performed in order to ensure such a guaranteed content of titanium carbides in the matrix, which affects the radiation swelling towards its decrease. Elastically distorted regions are formed on the carbide-matrix interface due to their coherence and significant positive volume mismatch of the crystal lattice parameters (+0.7 [9]), which serve as sinks for vacancies.
- TiC carbides trap helium bubbles and make them difficult to transform into pores.
- the titanium and carbon remaining in the solid solution make a significant contribution to the suppression of swelling both due to the positive effect of radiation-induced TiC carbides and due to the effect of individual titanium atoms in the solid solution.
- phase transformation y -> a in the process of irradiation of austenitic steels occurs due to a significant depletion of the matrix in austenite-forming elements, primarily nickel.
- the depletion of the austenite matrix with nickel is accompanied by increased swelling.
- the positive effect of increased nickel concentrations on the suppression of swelling was noted both for simple ternary alloys of the Fe-Cr-Ni system, and for complex alloyed industrial compositions, and the minimum swelling is noted at a nickel content in the range of 35-45%.
- a quantitative assessment of the degree of depletion of the austenitic matrix with nickel showed that at a swelling value of 8%, the depletion of nickel in the matrix is about 6% [12].
- the main element giving high corrosion resistance to steels is chromium.
- the role of chromium is to provide the passivation ability of steel.
- a protective passivating film is formed only when the chromium content in steel is more than 12.5%.
- the chromium content in the claimed grade is set in the range (15 - 16)%.
- Molybdenum is an element that reduces the diffusion mobility of various elements and increases creep resistance.
- alloying with molybdenum contributes to a decrease in the degree of segregation processes of alloying and impurity elements in the matrix during operation, as well as to an increase in the recrystallization temperature, which is important for the formation of the required grain score in the workpiece during forging.
- a decrease in the diffusion mobility of elements contributes, among other things, to a decrease in swelling, and an increase in creep resistance provides a higher resistance to stress corrosion cracking.
- silicon is used as one of the deoxidizers. Silicon has a diffusion mobility several orders of magnitude higher than nickel and other basic alloying elements of austenitic steel. The acceleration of diffusion in steels doped with silicon reduces the saturation with vacancies and, thus, decreases the rate of pore nucleation. Another mechanism of the influence of silicon as a sub-sized element is similar to nickel - silicon forms stable complexes with interstitial atoms and thereby increases the degree of their recombination with vacancies. However, during the formation of the g'-phase of N Si, silicon is removed from the solid solution, together with nickel, which most effectively suppresses swelling and stabilizes the g-phase. In the prototype 08X18H10T, the silicon content is limited to the top by 0.8%. Considering both the positive and negative effects of silicon, in the claimed brand, the silicon content is limited to (0.4 - 0.6)%.
- Manganese is used to remove oxygen and sulfur from steel. It has less segregation tendency than any other alloying element. Manganese favorably influences the quality of forgings over the entire carbon content range, with the exception of steels with very low carbon content, and also reduces the risk of red brittleness. Manganese has a beneficial effect on the ductility and weldability of steels. Manganese promotes the formation of austenite and therefore expands the austenitic region of the phase diagram. A high content of manganese (more than 2%) leads to an increased tendency to cracking and warping during quenching. In the claimed steel grade, the manganese content is limited by the level (1.5 - 2.0)%.
- the nitrogen content in the claimed steel is normalized as an impurity, since nitrogen leads to the formation of titanium nitrides and carbonitrides, on which deformation pores are formed [15].
- nitrogen reduces the energy of packing faults (EDF), which negatively affects the resistance of steel to stress corrosion cracking.
- EDF packing faults
- the inventive steel is alloyed with calcium in an amount of 0.001-0.003%, which is adsorbed on the surface of growing crystals during solidification, reducing the growth rate of metal crystal faces and thereby contributes to the formation of a more dispersed structure.
- Calcium binds sulfur into refractory compounds, sharply reducing the possibility of the formation of low-melting sulfides TiS and NiS at a super-equilibrium sulfur content.
- rare-earth metal REM
- Cerium and lanthanum REM additives cerium and lanthanum into the metal in a total amount of 0.001-0.005%, leads to grain refinement; cleans steel from oxygen, sulfur and neutralizes the harmful effects of non-ferrous metal impurities; improves the weldability of steel in terms of increasing resistance to the formation of "hot cracks" as a result of the binding of sulfur and oxygen to refractory compounds [16].
- Rare earth metals reduce the resistance to deformation during forging, increasing the manufacturability of steel in the manufacture of large-sized forgings. In addition, these metals reduce radiation swelling [9].
- Phosphorus has a high diffusion mobility and enhances the diffusion rate of the main steel elements.
- Secretions of RegP phosphides enhance the recombination of point radiation-induced defects at the precipitate-matrix interface due to high mismatch [9, 17]. Therefore, in the declared steel grade, phosphorus should not be considered as an impurity.
- the optimal phosphorus content in terms of reducing swelling is from 0.020% to 0.035% [12, 17].
- the phosphorus content can be limited to 0.035% as in the prototype.
- the sulfur content in the claimed brand is limited to 0.008%, which, in combination with microalloying with calcium, ensures almost complete absence of the formation of low-melting eutectics during the solidification of the ingot and, as a consequence, ensures its technological strength.
- the low sulfur content provides a low volume fraction of sulfides and, as a result, a high level of fracture toughness and impact toughness [19].
- the content of copper as an impurity, as in the prototype steel, is limited to 0.3% according to GOST 5632-72 [1] for steels not alloyed with copper.
- the elements tin, antimony, arsenic, bismuth and lead are impurities and their content in the proposed steel should not exceed 0.001%.
- the content of impurities in excess of the specified level negatively affects the service characteristics of the steel - impurities, when exposed to the operating temperature and radiation, which enhance diffusion, segregate at the grain boundaries and weaken their cohesive strength.
- the metal was smelted in vacuum induction furnaces. Casting into ingots was carried out in vacuum. The resulting metal was subjected to hot working with pressure on industrial press-forging equipment.
- the microstructure and radiation swelling of the irradiated layer of the samples were investigated by scanning and transmission electron microscopy.
- the metal of the forging of the claimed steel with 20% nickel has a swelling 1.3 times lower than that of the prototype.
- the claimed steel with a nickel content of 20% does not provide the required reduction of radiation swelling in comparison with the prototype by 2.4 times, and, therefore, the specified material does not ensure the guaranteed performance of the VVER TOP baffle during the design service life of 60 years.
- Irradiation in a metal ion accelerator for forgings N ° 3 and N ° 4 was carried out according to the regime simulating the irradiation of the VKU material in VVER-type reactors.
- the metal of the prototype (N2I forging) was irradiated in the same mode.
- FIG. 2 it can be seen that the swelling of the metal of forging No. 3 is 2.4 times lower than that of the prototype, and the swelling of the metal of forging No. 4 is 2.7 times lower than that of the prototype.
- FIG. 3 shows a comparison of the deformation diagrams of the metal for forging N «3 (without REM and calcium) and forging N ° 4 (with REM and calcium) at forging temperatures, and it can be seen that the resistance of steel with REM and calcium is lower.
- alloying steel with REM improves its manufacturability (Fig. 3).
- GOST 5632-2014 "Alloyed stainless steels and corrosion-resistant, heat-resistant and heat-resistant alloys", M., 2015, 54 p.
- Gamer F.A. Black C.A., Edwards D.J., Factors which control the swelling of Fe-Cr-Ni ternary austenitic alloys // J. Nucl. Mater., 1997, V. 245, 124-130 pp.
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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Abstract
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/257,277 US20210269905A1 (en) | 2019-04-15 | 2019-12-31 | Radiation-Resistant Austenitic Steel for an Internal Baffle for Pressurized Water Reactors |
BR112020026858A BR112020026858A2 (pt) | 2019-04-15 | 2019-12-31 | Aço austenítico resistente à radiação para revestimento interno para reatores de água pressurizada |
KR1020207037832A KR20210154708A (ko) | 2019-04-15 | 2019-12-31 | 가압수형 원자로(vver) 내부 구조물의 배플용 내방사선성 오스테나이트 스틸 |
CA3105268A CA3105268A1 (en) | 2019-04-15 | 2019-12-31 | Radiation-resistant austenite steel for in-vessel baffle |
EP19925353.5A EP3957762A1 (en) | 2019-04-15 | 2019-12-31 | Radiation-resistant austenitic steel for an internal baffle for pressurized water reactors |
CN201980043944.8A CN114207174A (zh) | 2019-04-15 | 2019-12-31 | 用于水-水动力反应堆内围壁的耐辐射奥氏体钢 |
JP2020573544A JP2022538196A (ja) | 2019-04-15 | 2019-12-31 | 原子炉容器内バッフル用の耐放射線性オーステナイト鋼 |
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RU2019111240A RU2703318C1 (ru) | 2019-04-15 | 2019-04-15 | Радиационно-стойкая аустенитная сталь для внутрикорпусной выгородки ввэр |
RU2019111240 | 2019-04-15 |
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WO2020214057A1 true WO2020214057A1 (ru) | 2020-10-22 |
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PCT/RU2019/001051 WO2020214057A1 (ru) | 2019-04-15 | 2019-12-31 | Радиационно-стойкая аустенитная сталь для внутрикорпусной выгородки ввэр |
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US (1) | US20210269905A1 (ru) |
EP (1) | EP3957762A1 (ru) |
JP (1) | JP2022538196A (ru) |
KR (1) | KR20210154708A (ru) |
CN (1) | CN114207174A (ru) |
BR (1) | BR112020026858A2 (ru) |
CA (1) | CA3105268A1 (ru) |
RU (1) | RU2703318C1 (ru) |
WO (1) | WO2020214057A1 (ru) |
Citations (4)
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RU2068022C1 (ru) * | 1994-06-17 | 1996-10-20 | Всероссийский научно-исследовательский институт неорганических материалов им.акад.А.А.Бочвара | Аустенитная сталь |
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RU2420600C1 (ru) * | 2009-09-24 | 2011-06-10 | Открытое акционерное общество "Высокотехнологический научно-исследовательский институт неорганических материалов имени академика А.А. Бочвара" | Особотонкостенная труба из аустенитной боросодержащей стали для оболочки твэла и способ ее получения |
US9347121B2 (en) * | 2011-12-20 | 2016-05-24 | Ati Properties, Inc. | High strength, corrosion resistant austenitic alloys |
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JP2897694B2 (ja) * | 1995-08-07 | 1999-05-31 | 株式会社日立製作所 | 耐応力腐食割れ性に優れたオーステナイト鋼及びその用途 |
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2019
- 2019-04-15 RU RU2019111240A patent/RU2703318C1/ru active
- 2019-12-31 KR KR1020207037832A patent/KR20210154708A/ko active Search and Examination
- 2019-12-31 CN CN201980043944.8A patent/CN114207174A/zh active Pending
- 2019-12-31 WO PCT/RU2019/001051 patent/WO2020214057A1/ru unknown
- 2019-12-31 US US17/257,277 patent/US20210269905A1/en active Pending
- 2019-12-31 BR BR112020026858A patent/BR112020026858A2/pt unknown
- 2019-12-31 EP EP19925353.5A patent/EP3957762A1/en not_active Ceased
- 2019-12-31 JP JP2020573544A patent/JP2022538196A/ja active Pending
- 2019-12-31 CA CA3105268A patent/CA3105268A1/en active Pending
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