US3303025A - Zirconium alloys - Google Patents

Zirconium alloys Download PDF

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Publication number
US3303025A
US3303025A US329856A US32985663A US3303025A US 3303025 A US3303025 A US 3303025A US 329856 A US329856 A US 329856A US 32985663 A US32985663 A US 32985663A US 3303025 A US3303025 A US 3303025A
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zirconium
alloy
alloys
steam
weight
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US329856A
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Raine Thomas
Robinson James Alan
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Associated Electrical Industries Ltd
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Associated Electrical Industries Ltd
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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
    • 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

Definitions

  • This invention relates to alloys of zirconium possessing a high resistance to corrosion in steam at a temperature within the range of approximately 280 C. to 500 C. and also in carbon dioxide, in air and in carbon dioxide/air mixtures.
  • a zirconium alloy in accordance with the present invention consists, essentially, by weight of 0.5 to 1.5% copper, 0.25 to 1.5% tungsten and 0.2 to 3.0% niobium.
  • alloys find particular use as the constituent material for the pressure tubes of steam generating, heavy water moderated, nuclear reactors.
  • Example 0 1,000 hours 2,000 hours Zircoloy-4 0. 124 0. 126 Zr, 2.5% Nb 0. 24 0.310 Zr, 05% Cu, 0.5% W 0.169 0.352 Zr, 0.5% 011, 0.5% W, 0.5% Nb 0. 210 0. 421 Z1, 1.0% Cu, 0.5% W, 1.0% Nb (Example 0). 0. 237 0. 428 Zr, 1.5% Cu, 0.5% W, 2.0% Nb 0.277 0. 466 Zr, 0.5% Cu, 0.5% b 0. 5 0.6 Zr, 1.5% Cu, 1.0% W, 0.5% Nb (Example (1) 0. 339 0.622 Zr, 0.5% Cu, 0.5% W, 1.0% Nb (Exa) 0. 469 0. 755
  • Example a 1,000 hours 2,000 hours Zr, 0.5% Cu, 0.5% W, 1.0% Nb
  • Example a 1. 50 2.11 Zr, 0.5% Cu, 0.5% W, 0.5% Nb 1.38 2. 40 Zr, 1.0% 011, 0.5% W, 1.0% Nb
  • Example c 1. 46 2. 55 Zr, 0.5% Cu, 0.5% W, 2.0% Nb 1.76 2.67 Zr, 1.5% Cu, 1.0% W, 0.5% Nb (Example (1). 1. 30 2. 79 Zr, 2.5% Nb 3. 21 5. 5 Zireoloy-4 Complete disintegration, Zr, 0.5% Cu, 0.5% W 25 hours Moist 002 at 700 C. and 0 p.s.i.g.-Weight gain, mgJcm.
  • a zirconium alloy consisting essentially by weight of References Cited by the Examiner tungsten, 1.0% niobium and the re- UNITED STATES PATENTS 3.
  • a zirconium alloy consisting essentially by weight of 2,924,518 2/1960 Rama 75 177 1.5 %d copper, 1.0% tungsten, 0.5% niobium and the re- 5 FOREIGN PATENTS main er zirocnium.
  • a zirconium alloy consisting essentially by weight of 630239 10/1961 Canada 0 5% copper 0 5% tungsten 1 0% niobium and the re- 1281198 11/1961 France 884,682 12/1961 Great Britain.
  • a zirconium alloy consisting essentially by weight of 10 DAVID RECK Primary Exammer- 1.0% copper, 1.5% tungsten, 0.5 niobium and the re- W, C, TOWNSEND, C, N, LOVELL, mainder zirconium. Assistant Examiners.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • High Energy & Nuclear Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Description

United States Patent.
P y No Drawing. Filed Dec. 11, 1963, Ser. No. 329,856 Claims priority, application Great Britain, Dec. 19, 1962, 47,937/ 62 5 Claims. (Cl. 75-177) This invention relates to alloys of zirconium possessing a high resistance to corrosion in steam at a temperature within the range of approximately 280 C. to 500 C. and also in carbon dioxide, in air and in carbon dioxide/air mixtures.
Zirconium base alloys containing 0.5% to 1.5%, by weight, copper and from 0.25% to 1.5%, by weight, tung sten, exhibit a considerable resistance to corrosion by carbon dioxide at elevated temperatures. These alloys also exhibit good creep properties at temperatures of about 550 C. Both creep resistance and resistance to corrosion may be greatly improved by heat treatment of the alloys, for example by heating at a temperature of about 950 C. followed by tempering at a temperature within the range 650 C. to 700 C. Such heat treatment results in an alloy with very high resistance to creep and with resistance to corrosion better than on annealed material, i.e., material heat treated by annealing at a temperature below 800 C.
For use in steam atmospheres at temperatures within the range 280 C. to 500 C., however, an alloy must have a high solubility for hydrogen. This is important for two reasons:
(a) If the alloy has a low solubility for hydrogen, rapid embrittlement caused by the precipitation of needles of zirconium hydride can occur during exposure of the alloy to high temperature steam, and
(b) Zirconium hydride needles precipitated at the specimen surface disrupt the protective oxide film, which normally develops on the surface, and expose the fresh underlying region of the alloy to the steam. This eifect, known as oxide spalling, leads to rapid corrosion of the alloy,
Disruption of the oxide film on the above mentioned zirconium-copper-tungsten alloys and by the above mentioned effects has been observed in high pressure steam at temperatures in the region of 500 C. It has now been found that this oxide spalling can be prevented by the addition of niobium to the ternary alloy.
A zirconium alloy in accordance with the present invention consists, essentially, by weight of 0.5 to 1.5% copper, 0.25 to 1.5% tungsten and 0.2 to 3.0% niobium.
By essentially is meant an alloy containing as well as the constituents specified any impurities inherently present in any of the alloy constituents and unspecified ingredients deliberately added to the alloy in order to change its composition but not materially aifecting the basic and novel properties.
These alloys find particular use as the constituent material for the pressure tubes of steam generating, heavy water moderated, nuclear reactors.
Conditions arise in steam generating, heavy water moderated nuclear reactors such that a member fabricated from a zirconium alloy is exposed on one side to steam at temperatures within the range 280 C. to 500 C. and to air, and a mixture of air and CO at different regions on the other side. Thus, any alloy used in this way must See have adequate resistance to corrosionin all three atmospheres. While resistance to corrosion of zirconium-copper-tungsten alloys in steam is increased by the addition of niobium, the resistance of the alloy to corrosion by air and by C0 is reduced. By suitable choice of composition of the quaternary alloys, according to the invention, their corrosion resistance in steam, in air, and in air/CO can be made adequate.
The following four examples are given of preferred quaternary alloys falling Within the range above specified as constituting the invention:
Example a0.5% Cu, 0.5% W, 1.0% Nb, remainder zirconium.
Example b1.0% Cu, 1.5% W, 0.5 Nb, remainder zirconium.
Example c1.0% Cu, 0.5% W, 1.0% Nb, remainder zirconium.
Example d-1.5% Cu, 1.0% W, 0.5% Nb, remainder zirconium.
Corrosion tests carried out on alloys within the ranges of composition claimed and on known commercially available alloys used in steam and C0 atmospheres respectively gave the following results. The alloys are listed in order of corrosion resistance under each condition.
Wet steam at 280 C. and 800 p.s.i.g.Weight Alloy gain, mg./cm.
1,000 hours 2,000 hours Zircoloy-4 0. 124 0. 126 Zr, 2.5% Nb 0. 24 0.310 Zr, 05% Cu, 0.5% W 0.169 0.352 Zr, 0.5% 011, 0.5% W, 0.5% Nb 0. 210 0. 421 Z1, 1.0% Cu, 0.5% W, 1.0% Nb (Example 0). 0. 237 0. 428 Zr, 1.5% Cu, 0.5% W, 2.0% Nb 0.277 0. 466 Zr, 0.5% Cu, 0.5% b 0. 5 0.6 Zr, 1.5% Cu, 1.0% W, 0.5% Nb (Example (1) 0. 339 0.622 Zr, 0.5% Cu, 0.5% W, 1.0% Nb (Example a) 0. 469 0. 755
Dry steam at 500 C. and 800 p.s.i.g./Weight gain,
mg. em.
1,000 hours 2,000 hours Zr, 0.5% Cu, 0.5% W, 1.0% Nb (Example a) 1. 50 2.11 Zr, 0.5% Cu, 0.5% W, 0.5% Nb 1.38 2. 40 Zr, 1.0% 011, 0.5% W, 1.0% Nb (Example c) 1. 46 2. 55 Zr, 0.5% Cu, 0.5% W, 2.0% Nb 1.76 2.67 Zr, 1.5% Cu, 1.0% W, 0.5% Nb (Example (1). 1. 30 2. 79 Zr, 2.5% Nb 3. 21 5. 5 Zireoloy-4 Complete disintegration, Zr, 0.5% Cu, 0.5% W 25 hours Moist 002 at 700 C. and 0 p.s.i.g.-Weight gain, mgJcm.
200 hours 1,000 hours Zr, 1 .5% Cu, 1.0% W, 0.5% Nb (Example (1). 5. 14.61 Zr, 0.5% Cu, 0.5% Mo 5. 00 17. 00 Zr, 1.0% Cu, 0 5% W, 1.0% Nb (Example 0). 6. 44 19. 74 Zr, 0.5% Cu, 54 Zr, 0.5% Cu, Zr, 0.5% Cu, Zr, 0.5% Cu, Zr, 2.5% Nb Zucoloy-4 What we claim is: 1. A zirconium alloy consisting essentially by weight of 0.5% to 1.5% copper, 0.25% to 1.5% tungsten, 0.2% to 3.0% niobium, and the remainder zirconium.
2. A zirconium alloy consisting essentially by weight of References Cited by the Examiner tungsten, 1.0% niobium and the re- UNITED STATES PATENTS 3. A zirconium alloy consisting essentially by weight of 2,924,518 2/1960 Rama 75 177 1.5 %d copper, 1.0% tungsten, 0.5% niobium and the re- 5 FOREIGN PATENTS main er zirocnium.
4. A zirconium alloy consisting essentially by weight of 630239 10/1961 Canada 0 5% copper 0 5% tungsten 1 0% niobium and the re- 1281198 11/1961 France 884,682 12/1961 Great Britain.
mainder zirconium.
5. A zirconium alloy consisting essentially by weight of 10 DAVID RECK Primary Exammer- 1.0% copper, 1.5% tungsten, 0.5 niobium and the re- W, C, TOWNSEND, C, N, LOVELL, mainder zirconium. Assistant Examiners.

Claims (1)

1. A ZIRCONIUM ALLOY CONSISTING ESSENTIALLY BY WEIGHT OF 0.5% TO 1.5% COPPER. 0.25% TO 1.5% TUNGSTEN, 0.2% TO 3.0% NIOBIUM, AND THE REMAINDER ZIRCONIUM.
US329856A 1962-12-19 1963-12-11 Zirconium alloys Expired - Lifetime US3303025A (en)

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Application Number Priority Date Filing Date Title
GB47937/62A GB1057369A (en) 1962-12-19 1962-12-19 Zirconium alloys

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2924518A (en) * 1957-07-26 1960-02-09 Vickers Electrical Co Ltd Zirconium alloys
CA630239A (en) * 1961-10-31 Government Of The United States Of America As Represented By The Secretary Of The Navy (The) Zirconium-base brazing alloy
GB884682A (en) * 1959-06-22 1961-12-13 Ass Elect Ind Zirconium alloys
FR1281198A (en) * 1960-03-01 1962-01-08 Ass Elect Ind Zirconium alloys used as construction materials in nuclear reactor fuel element assemblies

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB894156A (en) * 1960-03-01 1962-04-18 Ass Elect Ind Improvements relating to zirconium alloys

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA630239A (en) * 1961-10-31 Government Of The United States Of America As Represented By The Secretary Of The Navy (The) Zirconium-base brazing alloy
US2924518A (en) * 1957-07-26 1960-02-09 Vickers Electrical Co Ltd Zirconium alloys
GB884682A (en) * 1959-06-22 1961-12-13 Ass Elect Ind Zirconium alloys
FR1281198A (en) * 1960-03-01 1962-01-08 Ass Elect Ind Zirconium alloys used as construction materials in nuclear reactor fuel element assemblies

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GB1057369A (en) 1967-02-01
DE1238669B (en) 1967-04-13

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