CN105483443B - The zirconium ferrocolumbium of fuel for nuclear power plant involucrum cupric and germanium - Google Patents

The zirconium ferrocolumbium of fuel for nuclear power plant involucrum cupric and germanium Download PDF

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CN105483443B
CN105483443B CN201510902466.5A CN201510902466A CN105483443B CN 105483443 B CN105483443 B CN 105483443B CN 201510902466 A CN201510902466 A CN 201510902466A CN 105483443 B CN105483443 B CN 105483443B
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zirconium
fuel
nuclear power
ferrocolumbium
germanium
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CN105483443A (en
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张金龙
胡洋
王桢
王波阳
段文荣
姚美意
周邦新
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University of Shanghai for Science and Technology
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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
    • 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
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
    • G21C3/02—Fuel elements
    • G21C3/04—Constructional details
    • G21C3/06—Casings; Jackets
    • G21C3/07—Casings; Jackets characterised by their material, e.g. alloys
    • 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

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  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
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Abstract

The present invention relates to a kind of zirconium ferrocolumbiums can serve as the structural materials sulfur-bearing such as pressurized-water reactor nuclear power plant fuel can and grid spacer band, belong to Zirconium alloy material technical field.The chemical composition of the zircaloy is by weight percentage：0.5%~2.0%Nb, 0.1%~0.5%Fe, 0.01% ~ 0.1%Cu, 0.01% ~ 0.1%Ge, surplus Zr.Alloying element preferred scope is：0.5%~0.7%Nb, 0.1%~0.5%Fe, 0.01% ~ 0.1%Cu, 0.01% ~ 0.1%Ge.The zircaloy of the present invention shows excellent corrosion resistance in 400 DEG C/10.3 MPa superheated steams and 360 DEG C/18.6 MPa deionized waters, it is substantially better than Zr 1Nb 0.15Fe alloys, and processability is good, and the core structural materials such as fuel element cladding and grid spacer band can be used as in PWR of Nuclear Power Station.

Description

The zirconium ferrocolumbium of fuel for nuclear power plant involucrum cupric and germanium
Technical field
It can serve as the structural materials such as light water reactor fuel can and grid spacer band the present invention relates to one kind and contains The zirconium ferrocolumbium of copper and germanium, belongs to Zirconium alloy material technical field.
Background technology
The thermal neutron absorption cross section of zirconium is small, and adds zircaloy made of a small amount of alloying element with good high temperature resistant Aqueous corrosion performance, good comprehensive mechanical property and higher heat conductivility, current PWR Fuel element uniquely use Cladding materials, first of safety curtain when being reactor operation.In order to reduce the cost of nuclear power, the combustion for improving nuclear fuel is needed Consumption, must extend the refulling cycle of nuclear fuel assembly in this way.When fuel assembly needs to run in reactor core longer Between, thus more stringent requirements are proposed to the performance of fuel element cladding material zircaloy.Nuclear fuel element is in reactor core When middle work, by neutron irradiation, high-temperature high pressure water corrosion and wash away, burn into hydrogen embrittlement, creep, fatigue and irradiation damage etc. It is the main reason for causing zirconium alloy cladding to fail, the water-fast side corrosive nature of wherein zirconium alloy cladding is to influence fuel member The main factor of part service life.
Alloying is the effective way of exploitation advanced zirconium alloys, but since the fuel element cladding material in presurized water reactor needs There is low thermal neutron absorption cross section, thus the type and content that alloying element can be added in zircaloy are all very limited. The zircaloy developed in the world at present mainly has the big series of Zr-Sn, Zr-Nb and Zr-Sn-Nb tri-.In this three major controls zircaloy In by adding the alloying elements such as Fe, Cr, Ni, Cu after, form the Zr-2, Zr-4, Zr-2.5Nb of application prospect, The zircaloys such as the zircaloys such as E110, M5, ZIRLO, E635, and N18, N36 and HANA with application prospect.To Zr-Nb systems, The elements such as appropriate Cu, Ge are added in Zr-1%Nb alloys greatly improves the corrosion resistance of the alloy.In addition, by France The M5 alloys of Fa Matong companies research and development（Zr-1.0Nb-0.125~0.135O）It is (55-60) GWd/MTU's as design burn-up The cladding tubes of AFM-3G fuel assemblies, corrosion rate is small under high burnup, and suction hydrogen is fewer than improving Zr-4, and irradiation increases than improvement Zr-4 is low, and the general corrosion resistance performance ratio of the alloy is improved Zr-4 and improved.M5 alloys anti-pellet clad interaction ( PCI) performance is good, and to the corrosion resisting property of 347 DEG C of boracic lithium aqueous solutions, this, which is also current Daya Bay nuclear power plant of China, is made Cladding tube material.
In order to better adapt to the situation of China's nuclear power developing, the difference of alloying element is adjusted on the basis of existing zircaloy It is the effective way for developing advanced zirconium alloys to match or add other type alloying elements.
Invention content
The object of the present invention is to provide a kind of fine corrosion resistance and the good fuel for nuclear power plant involucrums of processing performance with containing The zirconium ferrocolumbium of copper and germanium, the zircaloy can be used as fuel element cladding and grid spacer item in PWR of Nuclear Power Station The structural materials such as band.
The purpose of the present invention is by adding alloy element copper on the basis of fuel for nuclear power plant involucrum zirconium ferrocolumbium （Cu）And germanium（Ge）And adjust existing niobium（Nb）Composition proportion come what is realized, its technical solution is as follows：
The zirconium ferrocolumbium of fuel for nuclear power plant involucrum cupric and germanium, the chemical composition of the zircaloy is by weight percentage For：0.5%~2.0%Nb, 0.1%~0.5%Fe, 0.01% ~ 0.1%Cu, 0.01% ~ 0.1%Ge, surplus Zr..
The zirconium ferrocolumbium of above-mentioned fuel for nuclear power plant involucrum cupric and germanium, alloying element are preferred by weight percentage Ranging from：0.5%~0.7%Nb, 0.1%~0.5%Fe, 0.01% ~ 0.1%Cu, 0.01% ~ 0.1%Ge.
The zirconium ferrocolumbium of above-mentioned cupric and germanium, preferred scope is alloying element by weight percentage：0.7%~ 1.1%Nb, 0.1%~0.5%Fe, 0.01% ~ 0.1%Cu, 0.01% ~ 0.1%Ge.
The zirconium ferrocolumbium of above-mentioned fuel for nuclear power plant involucrum cupric and germanium, alloying element are preferred by weight percentage Ranging from：1.1%~1.5%Nb, 0.1%~0.4%Fe, 0.01% ~ 0.1%Cu, 0.01% ~ 0.1%Ge.
The zirconium ferrocolumbium of above-mentioned cupric and germanium, preferred scope is alloying element by weight percentage：1.5%~ 2.0%Nb, 0.1%~0.4%Fe, 0.01% ~ 0.1%Cu, 0.01% ~ 0.1%Ge.
The zirconium ferrocolumbium of cupric and germanium of the present invention contains the other impurities element contained in core grade sponge zirconium.
The effect of the present invention：Application example provided by the invention show alloy in 400 DEG C/10.3 MPa superheated steams and When corroding in 360 DEG C/18.6 MPa deionized waters, very excellent corrosion resistance is shown, hence it is evident that be better than Zr-1Nb- 0.15Fe alloys：When corroding 340 days in 400 DEG C/10.3 MPa superheated steams, the surrosion of zircaloy of the present invention is 165.1 mg/dm2, and the surrosion of Zr-1Nb-0.15Fe alloys is up to 278.3 mg/dm2；In 360 DEG C/18.6 MPa deionized waters When corroding 310 days, the surrosion of zircaloy of the present invention is 70.3 mg/dm2, and the corrosion of Zr-1Nb-0.15Fe alloys increases It is up to 89.17 mg/dm again2.In addition, only adding a small amount of Cu and Ge elements in the alloying component of the present invention can significantly improve Corrosion resistance of the zircaloy in 400 DEG C/10.3 MPa superheated steams and 360 DEG C/18.6 MPa deionized waters, and have Good processing performance.
The fuel can zircaloy of commercial applications real so far（Zr-4, ZIRLO, M5 and E110 alloy）In Alloying element total amount is seldom, only accounts for the 1%~3% of alloy gross mass, remaining 97%~99% be zirconium, so each alloying element contains It is seldom to measure transformable range, and the variation of exactly this minimal amount of alloying element causes Corrosion Resistance of Zirconium Alloys prodigious Variation.For example, in 400 DEG C/10.3 MPa superheated steams, addition Bi can improve the Zr-Sn-Nb systems of high Nb and Zr-Nb systems close The corrosion resistance of gold, but the corrosion resistance of Zr-Sn systems Zr-4 alloys is made to be deteriorated.As it can be seen that adding same alloying element to not The affecting laws of homologous series Corrosion Resistance of Zirconium Alloys are different.
Specific implementation mode
The cupric of the fine corrosion resistance of the present invention and the zirconium ferrocolumbium of germanium are made with reference to embodiment further It is described in detail, but the present invention is not limited to following embodiments：
Embodiment 1
Referring to table 1, there is shown the ingredients of four kinds according to the present invention typical cuprics and the zirconium ferrocolumbium material of germanium Composition.
It is prepared in accordance with the following steps with the alloy material formed in table 1
(1) above-mentioned formula dispensing is pressed, the alloy pig of about 65g weights is smelted into vacuum non-consumable arc furnace, when melting fills height Straight argon gas shielded, and the uniform alloy pig of ingredient is made 6 times in alloy overturning melt back；
(2) above-mentioned alloy pig at 700 DEG C is subjected to multiple hot pressing, is processed into blank material, it is therefore an objective to is broken coarse As-cast grain structure；
(3) blank material is after scale removal and pickling, in a vacuum through 1030~1050 DEG C of β phase Homogenization Treatments It is air-cooled after 0.5~1 h；Through 700 DEG C of hot rollings after, first scale removal, pickling removal grease after hot rolling, then pass through in a vacuum 1030~1050 DEG C of β phases keep the temperature air-cooled after 0.5~1 h；
(4) multiple cold rolling is carried out after blank material is air-cooled, total cold roling reduction is more than 50%, finally carries out 580 DEG C in a vacuum 2 h of recrystallization annealing carries out pickling and deionized water cleaning before each intermediate annealing or recrystallization annealing.
By the zircaloy sample prepared by above-mentioned technique and the Zr-1Nb-0.15Fe alloy samples Jing Guo same preparation process It is put into autoclave, is corroded in 400 DEG C/10.3 MPa superheated steams and 360 DEG C/18.6 MPa deionized waters together Experiment, investigates their corrosion behavior, surrosion data are as shown in table 2, as can be seen from Table 2：In 400 DEG C/10.3 MPa Change when corroding in superheated steam, in the present invention Nb contents in zircaloy be respectively 0.74%, 1.00%, 1.33%, 1.62%Nb with And weightening of Fe contents when being 0.38% when alloy corrosion 340 days is respectively 165.1 mg/dm2、200.4 mg/dm2、198.4 mg/dm2、227.7 mg/dm2With 170.1 mg/dm2, Zr-1Nb-0.15Fe alloy samples are 278.3 mg/dm2；360 DEG C/18.6 when corroding in MPa deionized waters, change in the present invention Nb contents in zircaloy be respectively 0.74%, 1.00%, 1.33%, the weightening when content of 1.62%Nb and Fe is 0.38% when alloy corrosion 310 days is respectively 70.3 mg/dm2、84.3 mg/dm2、89.6 mg/dm2、83.0 mg/dm2With 79.5 mg/dm2, Zr-1Nb-0.15Fe alloy samples are 89.2 mg/dm2。 Excellent corrosion of the alloy of the present invention in 400 DEG C/10.3 MPa superheated steams and 360 DEG C/18.6 MPa deionized waters In Zr-1Nb-0.15Fe alloys.In alloying component of the present invention only need added in Zr-1Nb-0.15Fe alloys a small amount of Cu and Ge can improve corrosion resistance of the zircaloy in 400 DEG C/10.3 MPa superheated steams and 360 DEG C/18.6 MPa deionized waters Can, better corrosion resistance can be obtained by adjusting Nb, Fe composition proportion in right amount, and the processing performance of alloy is good.
Above-described embodiment, only section Example of the invention not are used for limiting the practical range of the present invention, thus it is all with The equivalence changes that content described in the claims in the present invention is done should all be included within scope of the invention as claimed.

Claims (3)

1. the cupric of fuel for nuclear power plant involucrum and the zirconium ferrocolumbium of germanium, it is characterised in that the chemical composition of the zircaloy is with weight Measuring percentages is：1.33%~2.0%Nb, 0.1%~0.5%Fe, 0.01%~0.1%Cu, 0.01%~0.1%Ge, Surplus is Zr.
2. the zirconium ferrocolumbium of fuel for nuclear power plant involucrum cupric as described in claim 1 and germanium, it is characterised in that：With weight Percentages, 1.33%~1.5%Nb, 0.1%~0.4%Fe, 0.01%~0.1%Cu, 0.01%~0.1%Ge.
3. the zirconium ferrocolumbium of fuel for nuclear power plant involucrum cupric as described in claim 1 and germanium, it is characterised in that：With weight Percentages, 1.5%~2.0%Nb, 0.1%~0.4%Fe, 0.01%~0.1%Cu, 0.01%~0.1%Ge.
CN201510902466.5A 2015-12-09 2015-12-09 The zirconium ferrocolumbium of fuel for nuclear power plant involucrum cupric and germanium Active CN105483443B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103451473A (en) * 2013-09-02 2013-12-18 上海大学 Zirconium alloy containing copper and germanium for nuclear power plant fuel cladding
CN103898361A (en) * 2012-12-27 2014-07-02 中国核动力研究设计院 Zirconium alloy for nuclear reactor core
GB2523976A (en) * 2012-12-27 2015-09-09 Nuclear Power Inst China Zirconium alloy for nuclear power

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103898361A (en) * 2012-12-27 2014-07-02 中国核动力研究设计院 Zirconium alloy for nuclear reactor core
GB2523976A (en) * 2012-12-27 2015-09-09 Nuclear Power Inst China Zirconium alloy for nuclear power
CN103451473A (en) * 2013-09-02 2013-12-18 上海大学 Zirconium alloy containing copper and germanium for nuclear power plant fuel cladding

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