CN116497247A - High-strength high-plasticity zirconium-niobium alloy for reactor and preparation method thereof - Google Patents
High-strength high-plasticity zirconium-niobium alloy for reactor and preparation method thereof Download PDFInfo
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- 229910001257 Nb alloy Inorganic materials 0.000 title claims abstract description 180
- GFUGMBIZUXZOAF-UHFFFAOYSA-N niobium zirconium Chemical compound [Zr].[Nb] GFUGMBIZUXZOAF-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000005242 forging Methods 0.000 claims abstract description 68
- 238000003723 Smelting Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000010955 niobium Substances 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003825 pressing Methods 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000010791 quenching Methods 0.000 claims description 27
- 230000000171 quenching effect Effects 0.000 claims description 27
- 239000006104 solid solution Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 20
- 230000006835 compression Effects 0.000 claims description 15
- 238000007906 compression Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 229910000734 martensite Inorganic materials 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 230000001276 controlling effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/186—High-melting or refractory metals or alloys based thereon of zirconium or alloys based thereon
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/08—Metals; Alloys; Cermets, i.e. sintered mixtures of ceramics and metals
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
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Abstract
The invention discloses a high-strength high-plasticity zirconium-niobium alloy for a reactor, which comprises the following components in percentage by mass: nb 2% -3.5%, and the balance of Zr and unavoidable impurities; the zirconium-niobium alloy has an ultrafine lath alpha and continuous net beta structure; the preparation method of the zirconium-niobium alloy comprises the following steps: 1. weighing intermediate alloy ingredients of nuclear-grade zirconium and Zr-Nb; 2. vacuum consumable smelting after pressing the electrode; 3. hot forging after sawing and peeling; 4. solution treatment; 5. and heating and preserving heat, and then compressing and deforming. The zirconium-niobium alloy has an ultrafine lath alpha and continuous net beta structure, improves the toughness and corrosion resistance of the zirconium-niobium alloy, obtains high-strength high-plasticity zirconium-niobium alloy, and meets the severe requirements of the service environment of a reactor; the invention obtains the lath-shaped alpha and grain boundary beta structure through heat treatment and thermal deformation processing, has fine alpha grain size and high dislocation density, endows the zirconium-niobium alloy with good comprehensive mechanical property and corrosion resistance, has simple process and is beneficial to industrial popularization.
Description
Technical Field
The invention belongs to the technical field of metal processing, and particularly relates to a high-strength high-plasticity zirconium-niobium alloy for a reactor and a preparation method thereof.
Background
The zirconium-niobium alloy has very small thermal neutron absorption section, good corrosion resistance, mechanical property and processability, is a main material of a nuclear power water reactor structural member, such as a fuel cladding, a pressure pipe, a container pipe and the like, and is also an ideal chemical structural material. With the continuous development of the nuclear industry field in China, the service environment of structural members in nuclear reactors is worse, and higher requirements are put on various performances of zirconium-niobium alloy materials, wherein the performances depend on the microstructure of the alloy, so that the regulation and control of the microstructure of the zirconium-niobium alloy is important.
The zirconium-niobium alloy structure consists of different phases and shapes, and is mainly related to alloy components and processing technology. The zirconium-niobium alloy can have various phase compositions at room temperature, such as an alpha-Zr phase, a beta-Nb phase, a martensite alpha', and the like, due to different Nb element contents. Because of different processing technologies, zirconium-niobium alloy also presents various tissue morphologies, such as cold deformation and high temperature recrystallization annealing can be used for preparing a binary structure of equiaxed alpha plus needle-shaped/strip-shaped alpha, beta-phase zone quenching and high temperature tempering can be used for preparing a basket structure of crossed needle-shaped/strip-shaped alpha, cold deformation and recrystallization annealing can be used for preparing an equiaxed alpha structure, and beta-phase zone annealing can be used for preparing a Winger body structure of parallel needle-shaped/strip-shaped alpha.
The stable structure of the zirconium-niobium alloy at room temperature can be mainly divided into a double-state structure, a basket structure, an equiaxed structure and a Wilmoschus structure, and different performances are shown, wherein the double-state structure has high plasticity and impact toughness, the basket structure has good high-temperature fracture toughness, the equiaxed structure has good plasticity, and the Wilmoschus structure has high fracture toughness and creep resistance. In addition, the presence of Nb in supersaturated state in alpha-Zr in the zirconium-niobium alloy is detrimental to corrosion resistance, while the presence of Nb in the second phase form is important for improving both corrosion resistance and mechanical properties of the alloy. Equiaxed alpha in the zirconium-niobium alloy mainly provides plasticity, needle-shaped/lath-shaped alpha provides toughness, and beta phase improves corrosion resistance and mechanical properties. Therefore, the zirconium-niobium alloy with good corrosion resistance and comprehensive mechanical properties can be prepared by regulating and controlling the microstructure.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the high-strength high-plasticity zirconium-niobium alloy for the reactor aiming at the defects of the prior art. The zirconium-niobium alloy has an ultrafine lath alpha and continuous net-shaped beta structure, the toughness of the zirconium-niobium alloy is improved through the ultrafine lath alpha tissue structure, meanwhile, the corrosion resistance of the zirconium-niobium alloy is synchronously improved through regulating and controlling the continuous net-shaped beta structure, the high-strength high-plasticity zirconium-niobium alloy is obtained, and the comprehensive performance of the zirconium-niobium alloy is optimally improved so as to meet the severe requirements of the service environment of a reactor.
In order to solve the technical problems, the invention adopts the following technical scheme: the high-strength high-plasticity zirconium-niobium alloy for the reactor is characterized by comprising the following components in percentage by mass: nb 2% -3.5%, and the balance of Zr and unavoidable impurities; the zirconium-niobium alloy has an ultrafine lath alpha and continuous net beta structure, the tensile strength of the zirconium-niobium alloy is 738-840 MPa, and the elongation is 12.3-25%.
In addition, the invention also discloses a method for preparing the high-strength high-plasticity zirconium-niobium alloy for the reactor, which is characterized by comprising the following steps of:
step one, batching: weighing nuclear-grade zirconium and Zr-Nb intermediate alloy which are free of oxide scale on the surface and are cleaned and dried as raw materials for batching according to nominal components of a target product zirconium-niobium alloy;
step two, vacuum consumable smelting: pressing the raw materials prepared in the first step into consumable electrodes after layering, and then carrying out vacuum consumable smelting on the consumable electrodes to obtain zirconium-niobium alloy ingots;
step three, hot forging: carrying out saw cutting and peeling on the zirconium-niobium alloy cast ingot obtained in the step two, and carrying out hot forging and air cooling to obtain a zirconium-niobium alloy forging;
step four, solution treatment: carrying out solution treatment on the zirconium-niobium alloy forging obtained in the step three, and carrying out water quenching or oil quenching to obtain a solid solution state zirconium-niobium alloy forging with a full martensitic alpha' structure;
fifthly, thermally deforming; and (3) heating and preserving heat, and then performing compression deformation, water quenching or oil quenching on the solid solution zirconium-niobium alloy forging obtained in the step (IV) to obtain the zirconium-niobium alloy.
The method is characterized in that the heating temperature of the hot forging in the third step is 1000-1050 ℃, and the heat preservation time is 0.5-1 h.
The method is characterized in that the solid solution treatment system in the step four is as follows: the temperature is 1000-1050 ℃, and the heat preservation time is 0.5-1 h.
The method is characterized in that the compression deformation process after heating and heat preservation in the fifth step comprises the following steps: firstly preserving heat for 5-30 min at 1050 ℃, then reducing the temperature to 750-840 ℃ for compression deformation, wherein the deformation amount is 40-75%, and the strain rate is 1s -1 ~10s -1 。
Compared with the prior art, the invention has the following advantages:
1. the zirconium-niobium alloy has an ultrafine lath alpha and continuous net-shaped beta structure, the toughness of the zirconium-niobium alloy is improved through the ultrafine lath alpha tissue structure, meanwhile, the corrosion resistance of the zirconium-niobium alloy is synchronously improved through regulating and controlling the continuous net-shaped beta structure, the high-strength high-plasticity zirconium-niobium alloy is obtained, and the comprehensive performance of the zirconium-niobium alloy is optimally improved so as to meet the severe requirements of the service environment of a reactor.
2. The zirconium-niobium alloy is prepared by the processes of proportioning, smelting, hot forging, solution treatment and thermal deformation in sequence, and the strip-shaped alpha and grain boundary beta structure is obtained by the solution heat treatment and thermal deformation, the alpha grain size is fine and the dislocation density is high, and the structure endows the zirconium-niobium alloy with good comprehensive mechanical property and corrosion resistance.
3. The invention has simple thermal processing technology, and no subsequent thermal treatment is needed after thermal deformation, thereby simplifying the preparation technology.
4. The thermal deformation process parameters of the invention comprise the deformation amount and the strain rate, have wide range and high practical value, and are beneficial to industrial popularization.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a microstructure of a solid solution zirconium niobium alloy forging prepared in example 1 of the present invention.
FIG. 2a is a microstructure of a zirconium niobium alloy prepared in example 1 of the present invention.
FIG. 2b is a composition diagram of a zirconium niobium alloy prepared in example 1 of the present invention.
FIG. 3 is an XRD diffraction pattern of a solid solution zirconium niobium alloy forging and zirconium niobium alloy as prepared in example 1 of the present invention.
FIG. 4 is a microstructure of the zirconium niobium alloy prepared in example 2 of the present invention.
FIG. 5 is a microstructure of the zirconium niobium alloy prepared in example 3 of the present invention.
FIG. 6 is a microstructure of the zirconium niobium alloy of the present invention as prepared in comparative example 1.
FIG. 7 is a microstructure of the zirconium niobium alloy prepared in example 4 of the present invention.
FIG. 8 is a microstructure of the zirconium niobium alloy of the present invention as prepared in comparative example 2.
FIG. 9 is a microstructure of the zirconium niobium alloy prepared in example 5 of the present invention.
FIG. 10 is a microstructure of the zirconium niobium alloy of the present invention as prepared in comparative example 3.
Detailed Description
Example 1
The high-strength high-plasticity zirconium-niobium alloy for the reactor comprises the following components in percentage by mass: nb 2.66%, H0.0005%, fe 0.01%, O0.086% and the balance Zr.
The preparation method of the high-strength high-plasticity zirconium-niobium alloy for the reactor comprises the following steps:
step one, batching: weighing nuclear-grade zirconium and Zr-Nb intermediate alloy which are free of oxide scale on the surface and are cleaned and dried as raw materials for batching according to nominal components of a target product zirconium-niobium alloy;
step two, vacuum consumable smelting: pressing the raw materials prepared in the first step into a consumable electrode after layering, and then carrying out vacuum consumable smelting on the consumable electrode for 4 times to obtain a zirconium-niobium alloy cast ingot;
step three, hot forging: carrying out sawing and peeling on the zirconium-niobium alloy cast ingot obtained in the step two, carrying out hot forging after preserving heat for 0.5h at 1025 ℃, and obtaining a zirconium-niobium alloy forging after air cooling;
step four, solution treatment: the zirconium niobium alloy forging piece obtained in the step three is subjected to solution treatment at 1025 ℃ for 0.5h, and after water quenching, the solid solution state zirconium niobium alloy forging piece with the full martensite alpha' structure is obtained, as shown in figure 1;
fifthly, thermally deforming; the solid solution state zirconium niobium alloy forging piece obtained in the step four is firstly preserved for 5min at 1025 ℃, then is reduced to 840 ℃ for compression deformation, the deformation amount is 60%, and the strain rate is 1s -1 And (5) water quenching to obtain the zirconium-niobium alloy.
The cooling mode after solution treatment in the fourth step can be replaced by oil quenching, and the cooling mode after compression deformation in the fifth step can be replaced by oil quenching.
As shown in FIG. 2a, the zirconium-niobium alloy prepared in this example has an ultrafine lath α of about 2.4 μm in length and about 1.2 μm in width and a grain boundary continuous network β structure.
Fig. 2b is a composition diagram of the zirconium niobium alloy prepared in this example, and it can be seen from fig. 2b that the zirconium niobium alloy structure prepared in this example has an Nb-lean alpha phase (points 1, 2, 3 in the figure) and an Nb-rich beta phase (points 4, 5, 6 in the figure).
Fig. 3 is an XRD diffraction pattern of the solid-solution zirconium niobium alloy forging and zirconium niobium alloy prepared in this example, and it is understood from fig. 3 that the solid-solution zirconium niobium alloy forging is mainly an α -Zr phase, and the zirconium niobium alloy is composed of an α -Zr phase and a β -Zr phase.
Example 2
The high-strength high-plasticity zirconium-niobium alloy for the reactor comprises the following components in percentage by mass: nb 2.66%, H0.0005%, fe 0.01%, O0.086% and the balance Zr.
The preparation method of the high-strength high-plasticity zirconium-niobium alloy for the reactor comprises the following steps:
step one, batching: weighing nuclear-grade zirconium and Zr-Nb intermediate alloy which are free of oxide scale on the surface and are cleaned and dried as raw materials for batching according to nominal components of a target product zirconium-niobium alloy;
step two, vacuum consumable smelting: pressing the raw materials prepared in the first step into a consumable electrode after layering, and then carrying out vacuum consumable smelting on the consumable electrode for 4 times to obtain a zirconium-niobium alloy cast ingot;
step three, hot forging: carrying out sawing and peeling on the zirconium-niobium alloy cast ingot obtained in the step two, carrying out hot forging after preserving heat for 0.5h at 1025 ℃, and obtaining a zirconium-niobium alloy forging after air cooling;
step four, solution treatment: the zirconium niobium alloy forging piece obtained in the step three is subjected to solution treatment at 1025 ℃ for 0.5h, and after water quenching, the solid solution state zirconium niobium alloy forging piece with the full martensite alpha' structure is obtained;
fifthly, thermally deforming; the solid solution state zirconium niobium alloy forging piece obtained in the step four is firstly preserved for 5min at 1025 ℃, then is reduced to 840 ℃ for compression deformation, the deformation amount is 75%, and the strain rate is 1s -1 And (5) water quenching to obtain the zirconium-niobium alloy.
As shown in FIG. 4, the zirconium-niobium alloy prepared in this example had a structure of a continuous network of ultrafine laths α and grain boundaries of about 3.4 μm in length and about 0.7 μm in width.
Example 3
The high-strength high-plasticity zirconium-niobium alloy for the reactor comprises the following components in percentage by mass: nb 2.66%, H0.0005%, fe 0.01%, O0.086% and the balance Zr.
The preparation method of the high-strength high-plasticity zirconium-niobium alloy for the reactor comprises the following steps:
step one, batching: weighing nuclear-grade zirconium and Zr-Nb intermediate alloy which are free of oxide scale on the surface and are cleaned and dried as raw materials for batching according to nominal components of a target product zirconium-niobium alloy;
step two, vacuum consumable smelting: pressing the raw materials prepared in the first step into a consumable electrode after layering, and then carrying out vacuum consumable smelting on the consumable electrode for 4 times to obtain a zirconium-niobium alloy cast ingot;
step three, hot forging: carrying out sawing and peeling on the zirconium-niobium alloy cast ingot obtained in the step two, carrying out hot forging after preserving heat for 0.5h at 1025 ℃, and obtaining a zirconium-niobium alloy forging after air cooling;
step four, solution treatment: the zirconium niobium alloy forging piece obtained in the step three is subjected to solution treatment at 1025 ℃ for 0.5h, and after water quenching, the solid solution state zirconium niobium alloy forging piece with the full martensite alpha' structure is obtained;
fifthly, thermally deforming; the solid solution state zirconium niobium alloy forging piece obtained in the step four is firstly preserved for 5min at 1025 ℃, then is reduced to 840 ℃ for compression deformation, the deformation amount is 40%, and the strain rate is 1s -1 And (5) water quenching to obtain the zirconium-niobium alloy.
As shown in FIG. 5, the zirconium-niobium alloy prepared in this example had a structure of a continuous network of ultrafine laths α and grain boundaries of about 1.7 μm in length and about 0.9 μm in width.
Comparative example 1
The high-strength high-plasticity zirconium-niobium alloy for the reactor of the comparative example comprises the following components in percentage by mass: nb 2.66%, H0.0005%, fe 0.01%, O0.086% and the balance Zr.
The preparation method of the high-strength high-plasticity zirconium-niobium alloy for the reactor of the comparative example comprises the following steps:
step one, batching: weighing nuclear-grade zirconium and Zr-Nb intermediate alloy which are free of oxide scale on the surface and are cleaned and dried as raw materials for batching according to nominal components of a target product zirconium-niobium alloy;
step two, vacuum consumable smelting: pressing the raw materials prepared in the first step into a consumable electrode after layering, and then carrying out vacuum consumable smelting on the consumable electrode for 4 times to obtain a zirconium-niobium alloy cast ingot;
step three, hot forging: carrying out sawing and peeling on the zirconium-niobium alloy cast ingot obtained in the step two, carrying out hot forging after preserving heat for 0.5h at 1025 ℃, and obtaining a zirconium-niobium alloy forging after air cooling;
step four, solution treatment: the zirconium niobium alloy forging piece obtained in the step three is subjected to solution treatment at 1025 ℃ for 0.5h, and after water quenching, the solid solution state zirconium niobium alloy forging piece with the full martensite alpha' structure is obtained;
fifthly, thermally deforming; the solid solution state zirconium niobium alloy forging piece obtained in the step four is firstly subjected to the temperature of 1025 DEG CPreserving heat for 5min, then cooling to 840 ℃ for compression deformation, wherein the deformation amount is 60%, and the strain rate is 0.1s -1 And (5) water quenching to obtain the zirconium-niobium alloy.
As shown in FIG. 6, the zirconium niobium alloy prepared in this comparative example has an equiaxed alpha and needle-like alpha' structure with a dimension of 1.67. Mu.m.
As can be seen by comparing FIG. 2a with FIG. 6, the strain rate is 0.1s compared to that used in comparative example 1 -1 Equiaxed alpha and needle-like alpha' structure of zirconium-niobium alloy prepared by hot deformation process of (1), strain rate 1s is adopted in example 1 -1 The zirconium-niobium alloy prepared by the thermal deformation process has superfine lath alpha and continuous netlike beta microstructure, which shows that the invention adjusts the structure morphology of the zirconium-niobium alloy by strictly controlling the technological parameter strain rate of thermal deformation processing, thereby obtaining the high-strength high-plasticity zirconium-niobium alloy.
Example 4
The high-strength high-plasticity zirconium-niobium alloy for the reactor comprises the following components in percentage by mass: nb 2.01%, H0.0007%, fe 0.01%, O0.085% and the balance Zr.
The preparation method of the high-strength high-plasticity zirconium-niobium alloy for the reactor comprises the following steps:
step one, batching: weighing nuclear-grade zirconium and Zr-Nb intermediate alloy which are free of oxide scale on the surface and are cleaned and dried as raw materials for batching according to nominal components of a target product zirconium-niobium alloy;
step two, vacuum consumable smelting: pressing the raw materials prepared in the first step into a consumable electrode after layering, and then carrying out vacuum consumable smelting on the consumable electrode for 4 times to obtain a zirconium-niobium alloy cast ingot;
step three, hot forging: carrying out sawing and peeling on the zirconium-niobium alloy cast ingot obtained in the step two, carrying out hot forging after preserving heat for 0.5h at 1050 ℃, and obtaining a zirconium-niobium alloy forging after air cooling;
step four, solution treatment: carrying out solution treatment on the zirconium-niobium alloy forging obtained in the step three at 1050 ℃ for 0.5h, and carrying out water quenching to obtain a solid solution state zirconium-niobium alloy forging with a full-martensitic alpha' structure;
fifthly, thermally deforming; forging the solid solution zirconium-niobium alloy obtained in the step fourThe piece is firstly insulated for 5min at 1050 ℃, then is reduced to 750 ℃ for compression deformation, the deformation amount is 60 percent, and the strain rate is 10s -1 And (5) water quenching to obtain the zirconium-niobium alloy.
As shown in FIG. 7, the zirconium-niobium alloy prepared in this example had a structure of a continuous network of ultrafine laths α and grain boundaries of about 0.9 μm in length and about 0.4 μm in width.
Comparative example 2
The high-strength high-plasticity zirconium-niobium alloy for the reactor of the comparative example comprises the following components in percentage by mass: nb 2.01%, H0.0007%, fe 0.01%, O0.085% and the balance Zr.
The preparation method of the high-strength high-plasticity zirconium-niobium alloy for the reactor of the comparative example comprises the following steps:
step one, batching: weighing nuclear-grade zirconium and Zr-Nb intermediate alloy which are free of oxide scale on the surface and are cleaned and dried as raw materials for batching according to nominal components of a target product zirconium-niobium alloy;
step two, vacuum consumable smelting: pressing the raw materials prepared in the first step into a consumable electrode after layering, and then carrying out vacuum consumable smelting on the consumable electrode for 4 times to obtain a zirconium-niobium alloy cast ingot;
step three, hot forging: carrying out sawing and peeling on the zirconium-niobium alloy cast ingot obtained in the step two, carrying out hot forging after preserving heat for 0.5h at 1050 ℃, and obtaining a zirconium-niobium alloy forging after air cooling;
step four, solution treatment: carrying out solution treatment on the zirconium-niobium alloy forging obtained in the step three at 1050 ℃ for 0.5h, and carrying out water quenching to obtain a solid solution state zirconium-niobium alloy forging with a full-martensitic alpha' structure;
fifthly, thermally deforming; the solid solution state zirconium niobium alloy forging piece obtained in the step four is firstly insulated for 5min at 1050 ℃, then is reduced to 880 ℃ for compression deformation, the deformation amount is 60%, and the strain rate is 10s -1 And (5) water quenching to obtain the zirconium-niobium alloy.
As shown in FIG. 8, the zirconium-niobium alloy prepared in this comparative example has a needle-like structure of α'.
Comparing fig. 7 and fig. 8, it can be seen that, compared with the needle-like α' structure of the zirconium-niobium alloy prepared by the thermal deformation process at 880 ℃ in comparative example 2, the zirconium-niobium alloy prepared by the thermal deformation process at 750 ℃ in example 4 has ultrafine lath α and continuous network β microstructure, which illustrates that the structure morphology of the zirconium-niobium alloy is adjusted by strictly controlling the temperature of the thermal deformation process parameters, thereby obtaining the high-strength and high-plasticity zirconium-niobium alloy.
Example 5
The high-strength high-plasticity zirconium-niobium alloy for the reactor comprises the following components in percentage by mass: nb 3.44%, H0.0005%, fe 0.01%, O0.055% and the balance Zr.
The preparation method of the high-strength high-plasticity zirconium-niobium alloy for the reactor comprises the following steps:
step one, batching: weighing nuclear-grade zirconium and Zr-Nb intermediate alloy which are free of oxide scale on the surface and are cleaned and dried as raw materials for batching according to nominal components of a target product zirconium-niobium alloy;
step two, vacuum consumable smelting: pressing the raw materials prepared in the first step into a consumable electrode after layering, and then carrying out vacuum consumable smelting on the consumable electrode for 4 times to obtain a zirconium-niobium alloy cast ingot;
step three, hot forging: carrying out sawing and peeling on the zirconium-niobium alloy cast ingot obtained in the step two, carrying out heat preservation at 1000 ℃ for 1h, and carrying out hot forging and air cooling to obtain a zirconium-niobium alloy forging;
step four, solution treatment: carrying out solution treatment on the zirconium-niobium alloy forging obtained in the step three at 1000 ℃ for 1h, and carrying out water quenching to obtain a solid solution state zirconium-niobium alloy forging with a full martensitic alpha' structure;
fifthly, thermally deforming; the solid solution state zirconium niobium alloy forging piece obtained in the step four is firstly insulated for 30min at 1050 ℃, then is reduced to 810 ℃ for compression deformation, the deformation amount is 60%, and the strain rate is 1s -1 And (5) water quenching to obtain the zirconium-niobium alloy.
As shown in FIG. 9, the zirconium-niobium alloy prepared in this example had a structure of a continuous network of ultrafine laths α and grain boundaries of about 1.1 μm in length and about 0.4 μm in width.
Comparative example 3
The high-strength high-plasticity zirconium-niobium alloy for the reactor of the comparative example comprises the following components in percentage by mass: nb 3.44%, H0.0005%, fe 0.01%, O0.055% and the balance Zr.
The preparation method of the high-strength high-plasticity zirconium-niobium alloy for the reactor of the comparative example comprises the following steps:
step one, batching: weighing nuclear-grade zirconium and Zr-Nb intermediate alloy which are free of oxide scale on the surface and are cleaned and dried as raw materials for batching according to nominal components of a target product zirconium-niobium alloy;
step two, vacuum consumable smelting: pressing the raw materials prepared in the first step into a consumable electrode after layering, and then carrying out vacuum consumable smelting on the consumable electrode for 4 times to obtain a zirconium-niobium alloy cast ingot;
step three, hot forging: carrying out sawing and peeling on the zirconium-niobium alloy cast ingot obtained in the step two, carrying out heat preservation at 1000 ℃ for 1h, and carrying out hot forging and air cooling to obtain a zirconium-niobium alloy forging;
step four, solution treatment: carrying out solution treatment on the zirconium-niobium alloy forging obtained in the step three at 1000 ℃ for 1h, and carrying out water quenching to obtain a solid solution state zirconium-niobium alloy forging with a full martensitic alpha' structure;
fifthly, thermally deforming; the solid solution state zirconium niobium alloy forging piece obtained in the step four is firstly preserved for 30min at 1000 ℃, then is reduced to 810 ℃ for compression deformation, the deformation amount is 20%, and the strain rate is 1s -1 And (5) water quenching to obtain the zirconium-niobium alloy.
As shown in FIG. 10, the zirconium niobium alloy prepared in this comparative example has an ultrafine lath α and needle-like α' structure having a size of about 2.3 μm.
Comparing fig. 9 and fig. 10, it can be seen that, compared with the ultra-fine lath α and needle-like α' structure of the zirconium-niobium alloy prepared by the thermal deformation process with 20% of deformation amount in comparative example 3, the zirconium-niobium alloy prepared by the thermal deformation process with 60% of deformation amount in example 5 has ultra-fine lath α and continuous network β microstructure, which shows that the invention adjusts the structure morphology of the zirconium-niobium alloy by strictly controlling the deformation amount of thermal deformation processing, thereby obtaining the high-strength and high-plasticity zirconium-niobium alloy.
The zirconium-niobium alloys of examples 1 to 5 and comparative examples 1 to 3 were cut out into tensile samples by slow wire cutting, performed according to the pin-fixed sheet type in ASTM E8, in order to ensure the reproducibility of dataAt least 3 samples were prepared for each example. Tensile test is carried out by an Instron 5582 double-upright-column electronic universal tester, and an extensometer is adopted in the whole process, and the strain rate is 110 -3 s -1 The test results are shown in Table 1.
As can be seen from Table 1, compared with the zirconium niobium alloys of comparative documents 1 to 3, the zirconium niobium alloys of examples 1 to 5 of the present invention have significantly improved yield strength and tensile strength and less decrease in elongation, which indicates that the present invention effectively adjusts the structure morphology of the zirconium niobium alloy by strictly controlling the deformation amount, temperature and strain rate of the heat deformation processing, thereby obtaining the high-strength and high-plastic zirconium niobium alloy.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (5)
1. The high-strength high-plasticity zirconium-niobium alloy for the reactor is characterized by comprising the following components in percentage by mass: nb 2% -3.5%, and the balance of Zr and unavoidable impurities; the zirconium-niobium alloy has an ultrafine lath alpha and continuous net beta structure, the tensile strength of the zirconium-niobium alloy is 738-840 MPa, and the elongation is 12.3-25%.
2. A method of making a high strength, high plasticity zirconium niobium alloy for a reactor as claimed in claim 1, comprising the steps of:
step one, batching: weighing nuclear-grade zirconium and Zr-Nb intermediate alloy which are free of oxide scale on the surface and are cleaned and dried as raw materials for batching according to nominal components of a target product zirconium-niobium alloy;
step two, vacuum consumable smelting: pressing the raw materials prepared in the first step into consumable electrodes after layering, and then carrying out vacuum consumable smelting on the consumable electrodes to obtain zirconium-niobium alloy ingots;
step three, hot forging: carrying out saw cutting and peeling on the zirconium-niobium alloy cast ingot obtained in the step two, and carrying out hot forging and air cooling to obtain a zirconium-niobium alloy forging;
step four, solution treatment: carrying out solution treatment on the zirconium-niobium alloy forging obtained in the step three, and carrying out water quenching or oil quenching to obtain a solid solution state zirconium-niobium alloy forging with a full martensitic alpha' structure;
fifthly, thermally deforming; and (3) heating and preserving heat, and then performing compression deformation, water quenching or oil quenching on the solid solution zirconium-niobium alloy forging obtained in the step (IV) to obtain the zirconium-niobium alloy.
3. The method according to claim 2, wherein the heating temperature of the hot forging in the third step is 1000 ℃ to 1050 ℃ and the heat preservation time is 0.5h to 1h.
4. The method according to claim 2, wherein the solution treatment schedule in step four is: the temperature is 1000-1050 ℃, and the heat preservation time is 0.5-1 h.
5. The method according to claim 2, wherein the compression deformation after heating and heat preservation in the fifth step comprises the following steps: firstly preserving heat for 5-30 min at 1050 ℃, then reducing the temperature to 750-840 ℃ for compression deformation, wherein the deformation amount is 40-75%, and the strain rate is 1s -1 ~10s -1 。
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