US3261682A - Zirconium alloys containing cerium and yttrium - Google Patents

Zirconium alloys containing cerium and yttrium Download PDF

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Publication number
US3261682A
US3261682A US236421A US23642162A US3261682A US 3261682 A US3261682 A US 3261682A US 236421 A US236421 A US 236421A US 23642162 A US23642162 A US 23642162A US 3261682 A US3261682 A US 3261682A
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Prior art keywords
zirconium
yttrium
cerium
alloys
consisting essentially
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Expired - Lifetime
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US236421A
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English (en)
Inventor
Rosler Ulrich
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Siemens Schuckertwerke AG
Siemens AG
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Siemens AG
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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

Definitions

  • My invention relates to zirconium alloys and, in a more particular aspect, to alloys suitable as structural material for use in nuclear reactors, such as for the envelopes or cans of nuclear fuel elements.
  • Structural materials in the interior of nuclear reactors are required to meet essentially the following four requirements:
  • zirconium alloys have been found to be well suitable, particularly in reactors using water as coolant.
  • Preferably employed has been the alloy known under the trade name Zircaloy-2 which, aside from zirconium, contains about 1.5% tin, 0.15% iron, 0.1% chromium and 0.05% nickel. (All percentages given in this specification are by weight.)
  • These alloying additions counteract the impairment in corrosion resistance of pure zirconium due to contaminating traces of other elements, mainly nitrogen.
  • Nuclear reactors equipped with fuel-element cans and structural parts of Zircaloy-2 or Zircaloy-4, the latter being nickel'free Zircaloy-2, can be operated with water temperatures only up to about 350 C. above which the materials are no longer sufficiently corrosion resistant. These temperatures do not afford employing in the reactor plant the improved, modern turbines of increased efficiency, because these turbines would make it desirable to convert to operation with superheated steam at temperatures between 400 and 500 C. and more.
  • zirconium-columbium (niobium) alloys with promising improved corrosion resistance in the just-mentioned temperature range as compared with Zircaloy-Z and Zircaloy-4.
  • zirconium-base alloy of 0.005 to 1% substance from the group consisting of cerium and yttrium, and one or more of the elements columbium, tin, copper, iron, chromium, nickel, molybdenum, tungsten, vanadium, tantalum and palladium, each in a quantity of up to about 5%, the remainder being substantially all of zirconium, which is understood to include impurities.
  • the total amount of the abovementioned addition elements, aside from cerium or yttrium, is less than and preferably less than 5% so that zirconium constitutes more than 90% and preferably more than 95% of the alloy, all percentages stated in this specification being by weight.
  • a cerium or yttrium content of 0.01 to 0.5%.
  • a favorable alloy composition contains 0.1 to 5%, preferably 0.3 to 2.5% columbium, 0.01 to 0.5% cerium, the remainder being substantially zirconium inclusive of impurities. Also applicable is the same composition if the cerium is substituted by 0.01 to 0.5% yttrium. In both cases the alloy may also contain at least one of the following additions within the stated ranges:
  • the increase in corrosion resistance under nuclear-reactor operating conditions achieved by the addition of cerium or yttrium is accompanied by the advantage that these additions do not appreciably increase the absorption cross section for thermal neutrons.
  • the absorption cross section of cerium is 0.7 barns/atom. Cerium is the only element from the series of the rare earths having a relatively low absorption cross section.
  • the absorption cross section for thermal neutrons in the case of yttrium is 1.38 barns/ atom, which is still rather low.
  • the corresponding absorption cross sections for zirconium and columbium are 0.18 and 1.1 barns/ atom respectively.
  • cerium or yttrium in the small quantities stated has only a negligible effect upon the absorption cross section of the entire Zr-Cb alloy. It will indeed be seen from the following test results that extremely slight quantities of cerium and yttrium additions suffice to secure the desired results.
  • the improved corrosion properties of the alloys according to the invention are exemplified by test results reported in the following tables.
  • the zircon alloys investigated were produced from zirconium sponge (reactor grade) and the alloying elements, by melting them together in an electric arc furnace under argon at a pressure of about 200 mm. Hg.
  • each alloy was twice remelted.
  • the alloy was subjected to cold rolling down to a sheet thickness of 0.8 mm.
  • Specimens were produced of about 3 cm. size. These were etched in the usual manner.
  • Employed as etching agent was the following composition: 45 volumetric percent HNO (65% concentration)+10 volumetric percent HF (40% concentration) +45 volumetric percent H O.
  • specimens 15 and 16 exhibit a considerable increase in weight, indicative of lower resistance to corrosion, in comparison with the corresponding yttrium-containing alloys of Table III. As in the case of the cerium addition, very slight amounts of yttrium may be suflicient for reducing the weight increase down to one-half of its original value.
  • a zirconium alloy consisting essentially of 0.1 to 5% columbium, 0.005 to 1.0% cerium, the balance consisting essentially of zirconium.
  • a zirconium alloy consisting essentially of 0.3 to 2.5% columbium, 0.01 to 0.5% cerium, the balance consisting essentially of zirconium.
  • a zirconium alloy consisting essentially of 0.3 to 2.5% columbium, 0.01 to 0.5% cerium, and at least one addition selected from the group consisting of Percent Sn 0.2 to 1 Cu 0.5 to 1.5 Fe 0.1 to 15 Cr 0.1 to 1.5 Ni 0.1 to 1.5 Mo 0.5 to 1 W 0.5 to 1 V 02 to 1 and the balance consisting essentially of zirconium.
  • a zirconium alloy consisting essentially of about 0.5% columbium, about 0.02 to about 0.5% cerium, the balance consisting essentially of zirconium.
  • a zirconium alloy consisting essentially of about 1% columbium, about 0.02% cerium, the balance consisting essentially of zirconium.
  • a zirconium alloy consisting essentially of 0.1 to 5% columbium, 0.005 to 1.0% yttrium, the balance consisting essentially of zirconium.
  • a zirconium alloy consisting essentially of 0.3 to 2.5 columbium, 0.01 to 0.5% yttrium, the balance consisting essentially of zirconium.
  • a zirconium alloy consisting essentially of 0.3 to 2.5 columbium, 0.01 to 0.5% yttrium, and at least one addition selected from the group consisting of and the balance consisting essentially of zirconium.
  • a zirconium alloy consisting essentially of about 0.5 to about 1% columbium, 0.02 to 0.5% yttrium, the balance consisting essentially of zirconium.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Catalysts (AREA)
US236421A 1962-09-29 1962-11-08 Zirconium alloys containing cerium and yttrium Expired - Lifetime US3261682A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DES81837A DE1202985B (de) 1962-09-29 1962-09-29 Zirkoniumlegierung

Publications (1)

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US3261682A true US3261682A (en) 1966-07-19

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DE (1) DE1202985B (de)
GB (1) GB1049380A (de)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2607141A1 (de) * 1975-02-25 1976-09-02 Gen Electric Verfahren zum waermebehandeln von gegenstaenden aus zirkonlegierung und vorrichtung zur durchfuehrung des verfahrens
DE2626941A1 (de) * 1975-06-26 1977-01-20 Gen Electric Bauteile aus korrosionsbestaendiger zirkoniumlegierung und verfahren zu deren herstellung
US4197145A (en) * 1974-12-23 1980-04-08 General Electric Company Zirconium-base alloy structural component for nuclear reactor and method
US4879093A (en) * 1988-06-10 1989-11-07 Combustion Engineering, Inc. Ductile irradiated zirconium alloy
US5019333A (en) * 1988-10-26 1991-05-28 Mitsubishi Metal Corporation Zirconium alloy for use in spacer grids for nuclear reactor fuel claddings
US5211774A (en) * 1991-09-18 1993-05-18 Combustion Engineering, Inc. Zirconium alloy with superior ductility
US5241571A (en) * 1992-06-30 1993-08-31 Combustion Engineering, Inc. Corrosion resistant zirconium alloy absorber material
US5867552A (en) * 1995-07-28 1999-02-02 General Electric Company Zirconium-based two-phase alloys for hydride resistant nuclear reactor components
US20080131306A1 (en) * 2006-12-05 2008-06-05 Korea Atomic Energy Research Institute Zirconium alloy composition having excellent corrosion resistance for nuclear applications and method of preparing the same
US20120201341A1 (en) * 2011-02-04 2012-08-09 Battelle Energy Alliance, Llc Zirconium-based alloys, nuclear fuel rods and nuclear reactors including such alloys, and related methods
CN110964946A (zh) * 2019-12-18 2020-04-07 佛山科学技术学院 一种锆合金
US20200157660A1 (en) * 2017-08-18 2020-05-21 Tokusen Kogyo Co., Ltd Alloy for biomedical use and medical product

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2642215B1 (fr) * 1989-01-23 1992-10-02 Framatome Sa Crayon pour assemblage combustible d'un reacteur nucleaire resistant a la corrosion et a l'usure
FR2702776B1 (fr) * 1993-03-19 1995-04-28 Commissariat Energie Atomique Alliages de zirconium résistant à la corrosion, utilisables notamment dans les réacteurs à eau.
US5475723A (en) * 1994-03-21 1995-12-12 General Electric Company Nuclear fuel cladding with hydrogen absorbing inner liner
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 (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2584030A (en) * 1947-02-07 1952-01-29 Polaroid Corp Light sensitive silver halide photographic product for image transfer and process utilizing the same
US2686717A (en) * 1949-04-16 1954-08-17 Polaroid Corp Photographic product comprising a sheet support and means for collecting liquid spread upon said support in excess of that required to cover a predetermined area of the support
GB715196A (en) * 1951-04-17 1954-09-08 Ozalid Co Ltd Improvements in or relating to the production of photographic images by migratory transfer
US2698237A (en) * 1954-08-16 1954-12-28 Polaroid Corp Photographic silver halide transfer product and process
GB724001A (en) * 1951-04-30 1955-02-16 Agfa Ag Photographic light sensitive silver halide emulsions and process using the same
US2765240A (en) * 1953-01-15 1956-10-02 Polaroid Corp Process for forming print-receiving elements
US2784084A (en) * 1954-07-12 1957-03-05 Jr Lyle L Marsh Zirconium ternary alloys
US2857276A (en) * 1954-11-23 1958-10-21 Polaroid Corp Photographic processes and compositions useful therein
US2897090A (en) * 1957-04-11 1959-07-28 Anken Chemical & Film Corp Heat-sensitive copying paper
US3000736A (en) * 1958-03-31 1961-09-19 Eastman Kodak Co Photographic silver halide diffusion transfer process
US3261683A (en) * 1960-05-02 1966-07-19 Gen Aniline & Film Corp Method of preparing transfer copies and compositions for use therein

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1111405B (de) * 1959-03-04 1961-07-20 Metallgesellschaft Ag Zirkonium-Legierung
GB894156A (en) * 1960-03-01 1962-04-18 Ass Elect Ind Improvements relating to zirconium alloys

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2584030A (en) * 1947-02-07 1952-01-29 Polaroid Corp Light sensitive silver halide photographic product for image transfer and process utilizing the same
US2686717A (en) * 1949-04-16 1954-08-17 Polaroid Corp Photographic product comprising a sheet support and means for collecting liquid spread upon said support in excess of that required to cover a predetermined area of the support
GB715196A (en) * 1951-04-17 1954-09-08 Ozalid Co Ltd Improvements in or relating to the production of photographic images by migratory transfer
GB724001A (en) * 1951-04-30 1955-02-16 Agfa Ag Photographic light sensitive silver halide emulsions and process using the same
US2765240A (en) * 1953-01-15 1956-10-02 Polaroid Corp Process for forming print-receiving elements
US2784084A (en) * 1954-07-12 1957-03-05 Jr Lyle L Marsh Zirconium ternary alloys
US2698237A (en) * 1954-08-16 1954-12-28 Polaroid Corp Photographic silver halide transfer product and process
US2857276A (en) * 1954-11-23 1958-10-21 Polaroid Corp Photographic processes and compositions useful therein
US2897090A (en) * 1957-04-11 1959-07-28 Anken Chemical & Film Corp Heat-sensitive copying paper
US3000736A (en) * 1958-03-31 1961-09-19 Eastman Kodak Co Photographic silver halide diffusion transfer process
US3261683A (en) * 1960-05-02 1966-07-19 Gen Aniline & Film Corp Method of preparing transfer copies and compositions for use therein

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4197145A (en) * 1974-12-23 1980-04-08 General Electric Company Zirconium-base alloy structural component for nuclear reactor and method
DE2607141A1 (de) * 1975-02-25 1976-09-02 Gen Electric Verfahren zum waermebehandeln von gegenstaenden aus zirkonlegierung und vorrichtung zur durchfuehrung des verfahrens
DE2626941A1 (de) * 1975-06-26 1977-01-20 Gen Electric Bauteile aus korrosionsbestaendiger zirkoniumlegierung und verfahren zu deren herstellung
US4268586A (en) * 1975-06-26 1981-05-19 General Electric Company Corrosion resistant zirconium alloy structural components and process
US4879093A (en) * 1988-06-10 1989-11-07 Combustion Engineering, Inc. Ductile irradiated zirconium alloy
US5019333A (en) * 1988-10-26 1991-05-28 Mitsubishi Metal Corporation Zirconium alloy for use in spacer grids for nuclear reactor fuel claddings
US5211774A (en) * 1991-09-18 1993-05-18 Combustion Engineering, Inc. Zirconium alloy with superior ductility
US5241571A (en) * 1992-06-30 1993-08-31 Combustion Engineering, Inc. Corrosion resistant zirconium alloy absorber material
US5867552A (en) * 1995-07-28 1999-02-02 General Electric Company Zirconium-based two-phase alloys for hydride resistant nuclear reactor components
US20080131306A1 (en) * 2006-12-05 2008-06-05 Korea Atomic Energy Research Institute Zirconium alloy composition having excellent corrosion resistance for nuclear applications and method of preparing the same
US20120201341A1 (en) * 2011-02-04 2012-08-09 Battelle Energy Alliance, Llc Zirconium-based alloys, nuclear fuel rods and nuclear reactors including such alloys, and related methods
US8831166B2 (en) * 2011-02-04 2014-09-09 Battelle Energy Alliance, Llc Zirconium-based alloys, nuclear fuel rods and nuclear reactors including such alloys, and related methods
US20200157660A1 (en) * 2017-08-18 2020-05-21 Tokusen Kogyo Co., Ltd Alloy for biomedical use and medical product
US11692244B2 (en) * 2017-08-18 2023-07-04 Tokusen Kogyo Co., Ltd. Alloy for biomedical use and medical product
CN110964946A (zh) * 2019-12-18 2020-04-07 佛山科学技术学院 一种锆合金

Also Published As

Publication number Publication date
DE1202985B (de) 1965-10-14
GB1049380A (en) 1966-11-23

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