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WO1995018874A1 - Alliage de zirconium - Google Patents

Alliage de zirconium Download PDF

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Publication number
WO1995018874A1
WO1995018874A1 PCT/SE1994/001254 SE9401254W WO9518874A1 WO 1995018874 A1 WO1995018874 A1 WO 1995018874A1 SE 9401254 W SE9401254 W SE 9401254W WO 9518874 A1 WO9518874 A1 WO 9518874A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
per cent
content
zirconium
tin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/SE1994/001254
Other languages
English (en)
Inventor
Peter Rudling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Westinghouse Electric Sweden AB
Original Assignee
ASEA Atom AB
ABB Atom AB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ASEA Atom AB, ABB Atom AB filed Critical ASEA Atom AB
Priority to AU14291/95A priority Critical patent/AU1429195A/en
Publication of WO1995018874A1 publication Critical patent/WO1995018874A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • G21C3/30—Assemblies of a number of fuel elements in the form of a rigid unit
    • G21C3/32—Bundles of parallel pin-, rod-, or tube-shaped fuel elements
    • G21C3/34—Spacer grids
    • 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 field of zirconium alloys for nuclear fuel components for light-water reactors.
  • the new alloy is a further development of zirconium alloys containing alloying elements from the group tin, iron, chromium, nickel, niobium, vanadium, silicon, and oxygen.
  • zirconium alloys as construction material for nuclear fuel components such as cladding tubes, boxes, spacers, guide tubes, etc.
  • the general requirements on these zirconium alloys are that they should have a low neutron absorption cross section, good mechanical properties such as strength, ductility, creep resistance and good corrosion resistance in a light-water reactor environment, and a low hydrogen absorption in connection with the corrosion.
  • a very large number of alloys have been developed to attempt to fulfil these requirement as well as possible or to attempt to obtain an alloy which is considerably improved with respect to any of these requirements.
  • the alloys which are most used as construction material are Zircaloy 2 and Zircaloy 4, which consist of zirconium containing 1.2 - 1.7 per cent by weight tin, 0.07 - 0.20 per cent by weight iron, 0.05 - 0.15 per cent by weight chromium, 0.03 - 0.08 per cent by weight nickel, 0.09 - 0.16 per cent by weight oxygen and ⁇ 1.2 - 1.7 per cent by weigh tin, 0.18 - 0.24 per cent by weight iron, 0.07 - 0.13 per cent by weight chromium, and 0.09 - 0.16 per cent by weight oxygen, respectively.
  • zirconium alloys are known contai- ning 0.5 to 2.0 % niobium, up to 1.5 % tin and up to 0.25 % of a third element such as iron, chromium, molybdenum, vanadium, copper, nickel, or tungsten.
  • This alloy is, in principle, a zirconium-niobium alloy with addition of tin up to 1.5 % and with a small addition ( ⁇ 0.25 %) of a third sub ⁇ stance.
  • a phase transformation to ⁇ phase is performed at 610°C.
  • the ductility of the material in ⁇ phase is worse than in ⁇ phase, which means that a structural part in a material with a lower phase transformation temperature is given worse proper ⁇ ties at a heavy increase in temperature in the core, such as at a "Loss of Coolant Accident".
  • US 4 233 149 describes a zirconium alloy consisting of zir ⁇ conium and 0.05 - 3.0 % tin, 0.001 - 4.5 % hafnium, 0.001 - 1.0 % iron, 0.001 - 1.0 % chromium, 0.001 - 1.0 % nickel, 0.05 - 0.5 % oxygen, 0.001 - 0.05 % nitrogen, 0.001 - 0.2 % of one or more elements from the group copper, cobalt, cadmium, manganese, aluminium, titanium, silicon, carbon, phosphorus, molybdenum, bismuth, vanadium, antimony, niobium, tungsten, and boron.
  • This alloy is intended to constitute anode material for anodizing aluminium.
  • the alloy is produced to improve the current yield, the abrasion resistance and the corrosion resistance in electrolytes such as sulphuric acid, for anodi ⁇ zing aluminium and not a zirconium alloy intended to be used as construction material for nuclear fuel components.
  • a zirconium alloy for nuclear fuel components is described in US 4 981 527 and consists of zirconium with 0.1 - 0.35 % iron, 0.07 - 0.4 % vanadium, 0.05 - 0.3 % oxygen, less than 0.25 % tin and less than 0.25 % niobium.
  • the low contents ( ⁇ 0.25 %) of tin and niobium are stated to be of importance for achieving a good corrosion resistance of the alloy.
  • the creep properties of this alloy are very inferior compared with, for example, Zircaloy 2 or 4. The reason is that the alloy has a low content of alloying additives and is therefore soft.
  • the patent specification CA 859 053 describes a zirconium- niobium-beryllium alloy which may be alloyed with up to 10 per cent by weight of at least one element from the group tin, copper, iron, chromium, molybdenum, vanadium, tungsten, tantalum, nickel, yttrium, antimony and tellurium.
  • the alloy contains 0.005 - 1.0 per cent by weight beryllium, which has a very low neutron absorption cross section but which is exceedingly poisonous and difficult to handle when manufac ⁇ turing an alloy.
  • the present invention relates to a zirconium alloy, for components included in nuclear fuel elements, with improved properties with respect to the absorption of hydrogen released during the corrosion, in combination with good strength and creep properties.
  • the invention is an improvement of known zirconium alloys based on zirconium with alloying addition of at least tin, iron, chromium, nickel and silicon, and is based on the realization that the hydrogen absorption for a zirconium alloy based on zirconium-tin-iron-chromium-nickel-silicon can be considerably reduced by small additions of vanadium.
  • niobium It is also possible to add small quantities of niobium to the alloy. However, the niobium content should be maintained low to avoid phase transformation at 610 °C.
  • These alloys based on zirconium-tin-iron-chromium-nickel- silicon and with addition of vanadium or vanadium and niobium have good strength in spite of the fact that the tin content may be lower than the standard value for Zircaloy 2, 4. This is possible because vanadium, besides affecting the hydrogen absorption, also has a solution-hardening effect. Also, the combination of iron, chromium and nickel and, where appli ⁇ cable, also niobium contributes to increase the strength.
  • the zirconium alloy according to the invention comprises, in addition to zirconium and normal contents of impurities for reactor-grade zirconium, also the alloying elements tin, iron, chromium, nickel, silicon, oxygen and vanadium, or vanadium and niobium.
  • the total content of tin, iron, nickel, chromium and silicon is at least 0.54 per cent by weight and at most 2.15 per cent by weight, of which the content of tin is at least 0.3 per cent by weight, the content of iron at least 0.07 per cent by weight, the content of chromium 0.05 per cent by weight, the content of nickel at least 0.03 per cent by weight, and the content of silicon at least 0.005 per cent by weight.
  • the alloy contains 0.015 to 0.30 per cent by weight vanadium or 0.015 to 0.30 per cent by weight vanadium and 0.015 to 0.30 per cent niobium.
  • the alloy according to the invention makes it possible for nuclear fuel components such as cladding tubes or spacers to obtain good strength properties in combination with good corrosion resistance and a low propensity to absorb hydrogen in connection with the corrosion process.
  • Absorption of hydrogen means that the material is embrittled when the hydrogen is precipitated in the form of needle-shaped hydrides. This embrittlement reduces the capacity of the material to withstand impacts, vibrations, and the like, which may arise in operation or when handling the fuel in connection with refuelling or storage of spent fuel.
  • composition of the alloy is such that it has a higher phase transformation temperature than the conventional resistant zirconium-niobium alloys which exhibit a decreasing ductility at temperatures exceeding about 600 °C.
  • the manufacture of nuclear fuel components is usually performed by means of hot-working, for example forging or hot- rolling of a blank.
  • Cladding tubes are manufactured by extruding a blank and then cold-rolling it in several steps with intermediate heat treatments and a final heat treatment.
  • Flat products for manufacturing boxes or spacers are produced by hot- and cold-rolling to a suitable dimension and by heat treatments between the cold-rolling operations, and a final heat treatment.
  • the manufacture of the alloy according to the invention is performed in the most advantageous manner by allowing all the hot-working and heat-treatment operations to take place in the ⁇ phase range. This provides the most favourable effect on the corrosion properties of the alloy. It is therefore advan ⁇ tageous with an alloy with a low niobium content to avoid initiating the phase transformation to ⁇ phase as early as at
  • cladding tubes according to the inven- tion may be manufactured from a zirconium alloy according to the above and that it is favourable to heat-treat the cladding tubes between the cold-rolling operations at a temperature below 600 °C.
  • the alloy according to the invention according to other methods for manufacturing zirconium-base alloys, which may mean that heat treatments are carried out in the ⁇ + ⁇ phase range or in the ⁇ phase range, so-called ⁇ quenching.
  • An alloy for cladding tubes intended for boiling or pressurized-water reactors consists of zirconium with 0.5 to 1.7 per cent by weight tin, 0.07 to 0.20 per cent by weight iron, 0.05 to 0.15 per cent by weight chromium, 0.03 to 0.08 per cent by weight nickel, 0.005 to 0.05 per cent by weight silicon, 0.09 to 0.16 per cent by weight oxygen, 0.015 to 0.30 per cent by weight vanadium and impurities in quantities normally occurring for reactor-grade zirconium.
  • the cladding tubes may be manufactured in conventional manner by means of extrusion and a number of cold-rolling steps alternating with heat treatments and a final heat treatment to impart optimum properties to the finished cladding tube.
  • Another alloy composition according to the invention which may be used for manufacturing cladding tubes, is an alloy consisting of zirconium with 0.03 to 1.0 per cent by weight tin, 0.07 to 0.70 per cent by weigh iron, 0.05 to 0.15 per cent by weight chromium, 0.16 to 0.40 per cent by weight nickel, 0.015 to 0.05 per cent by weight silicon, 0.09 to 0.16 per cent by weight oxygen, 0.015 to 0.30 per cent by weight vanadium, 0.015 to 0.30 per cent by weight niobium, and impurities in quantities normally occurring for reactor-grade zirconium.
  • the cladding tubes may be manufactured by means of extrusion and four cold-working steps with intermediate heat treatments at temperatures lower than 600 °C and a final heat treatment at 450 to 700 °C.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Catalysts (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

L'invention concerne un alliage de zirconium pour constituants de combustible nucléaire, tels que des tubes de gainage, des pièces d'écartement, des boîtes, etc., présentant de meilleures propriétés d'absorption de l'hydrogène dégagé au cours de la corrosion, associées à une bonne solidité et à une bonne résistance au fluage. L'alliage contient du zirconium et de l'étain, du fer, du nickel, du chrome et du silicium, la teneur totale s'élevant au moins à 0,54 % en poids et au plus à 2,15 % en poids. La teneur en étain s'élève au moins à 53 %, la teneur en fer, à au moins 0,07 %, la teneur en nickel, à au moins 0,03 %, la teneur en chrome, à au moins 0,05 %, et la teneur en silicium, à au moins 0,005 %. L'alliage contient également entre 0,15 et 0,30 % de vanadium et entre 0,015 et 0,30 % de niobium.
PCT/SE1994/001254 1994-01-03 1994-12-27 Alliage de zirconium Ceased WO1995018874A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU14291/95A AU1429195A (en) 1994-01-03 1994-12-27 Zirconium alloy

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9400010A SE9400010D0 (sv) 1994-01-03 1994-01-03 Zirkoniumlegering
SE9400010-6 1994-01-03

Publications (1)

Publication Number Publication Date
WO1995018874A1 true WO1995018874A1 (fr) 1995-07-13

Family

ID=20392494

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1994/001254 Ceased WO1995018874A1 (fr) 1994-01-03 1994-12-27 Alliage de zirconium

Country Status (3)

Country Link
AU (1) AU1429195A (fr)
SE (1) SE9400010D0 (fr)
WO (1) WO1995018874A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2776821A1 (fr) * 1998-03-31 1999-10-01 Framatome Sa Procede de fabrication d'un tube pour assemblage de combustible nucleaire
KR100480529B1 (ko) * 1996-04-16 2005-07-11 꽁빠니 유로펜 뒤 지르코니움 세쥐스 내크리프성과물및증기에의한부식에대한내성이있는지르코늄계합금,이의제조방법및이로부터제조된원자로용부재
CN103898362A (zh) * 2012-12-27 2014-07-02 中国核动力研究设计院 一种水冷核反应堆用锆基合金
CN111254315A (zh) * 2020-03-30 2020-06-09 上海核工程研究设计院有限公司 一种耐疖状腐蚀的Zr-Sn-Fe-Cr-O合金及其制备方法
EP3907742A1 (fr) * 2020-05-07 2021-11-10 Westinghouse Electric Sweden AB Tube de revêtement pour une barre de combustible pour un réacteur nucléaire, barre de combustible et ensemble combustible

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113820191B (zh) * 2021-10-19 2024-01-19 西安西部新锆科技股份有限公司 一种高均匀性锆合金标准物质及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017336A (en) * 1988-01-22 1991-05-21 Mitsubishi Kinzoku Kabushiki Kaisha Zironium alloy for use in pressurized nuclear reactor fuel components
US5241571A (en) * 1992-06-30 1993-08-31 Combustion Engineering, Inc. Corrosion resistant zirconium alloy absorber material
US5244514A (en) * 1992-02-14 1993-09-14 Combustion Engineering, Inc. Creep resistant zirconium alloy

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017336A (en) * 1988-01-22 1991-05-21 Mitsubishi Kinzoku Kabushiki Kaisha Zironium alloy for use in pressurized nuclear reactor fuel components
US5244514A (en) * 1992-02-14 1993-09-14 Combustion Engineering, Inc. Creep resistant zirconium alloy
US5241571A (en) * 1992-06-30 1993-08-31 Combustion Engineering, Inc. Corrosion resistant zirconium alloy absorber material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, Vol. 10, No. 383, C-393; & JP,A,61 174 347 (HITACHI LTD), 6 August 1986. *
PATENT ABSTRACTS OF JAPAN, Vol. 15, No. 154, C-825; & JP,A,03 031 438 (NIPPON NUCLEAR FUEL DEV CO LTD), 12 February 1991. *
ZIRCONIUM IN THE NUCLEAR INDUSTRY: NINTH INT. SYMPOSIUM, ASTM STP 1132, Philadelphia, ISOBE et al., "Development of Highly Corrosion Restistant Zirconium-Base Alloys", p 346-367. *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100480529B1 (ko) * 1996-04-16 2005-07-11 꽁빠니 유로펜 뒤 지르코니움 세쥐스 내크리프성과물및증기에의한부식에대한내성이있는지르코늄계합금,이의제조방법및이로부터제조된원자로용부재
FR2776821A1 (fr) * 1998-03-31 1999-10-01 Framatome Sa Procede de fabrication d'un tube pour assemblage de combustible nucleaire
WO1999050854A1 (fr) * 1998-03-31 1999-10-07 Framatome Alliage et tube pour assemblage de combustible nucleaire et procede de fabrication d'un tel tube
KR100680886B1 (ko) * 1998-03-31 2007-02-09 프라마톰 아엔페 핵 연료 집합체용 합금과 튜브 및 그 제조방법
CN103898362A (zh) * 2012-12-27 2014-07-02 中国核动力研究设计院 一种水冷核反应堆用锆基合金
CN111254315A (zh) * 2020-03-30 2020-06-09 上海核工程研究设计院有限公司 一种耐疖状腐蚀的Zr-Sn-Fe-Cr-O合金及其制备方法
EP3907742A1 (fr) * 2020-05-07 2021-11-10 Westinghouse Electric Sweden AB Tube de revêtement pour une barre de combustible pour un réacteur nucléaire, barre de combustible et ensemble combustible
WO2021223925A1 (fr) 2020-05-07 2021-11-11 Westinghouse Electric Sweden Ab Tube de gainage pour une tige de combustible pour un réacteur nucléaire, tige de combustible et ensemble combustible
JP2023525484A (ja) * 2020-05-07 2023-06-16 ウェスティングハウス エレクトリック スウェーデン アーベー 原子炉用の燃料棒のための被覆管、燃料棒及び燃料集合体

Also Published As

Publication number Publication date
SE9400010D0 (sv) 1994-01-03
AU1429195A (en) 1995-08-01

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