US3645800A - Method for producing wrought zirconium alloys - Google Patents

Method for producing wrought zirconium alloys Download PDF

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US3645800A
US3645800A US515297A US3645800DA US3645800A US 3645800 A US3645800 A US 3645800A US 515297 A US515297 A US 515297A US 3645800D A US3645800D A US 3645800DA US 3645800 A US3645800 A US 3645800A
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alloy
temperature
percent
alpha
hot working
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James W Mock
William C Bowen
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CBS Corp
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Westinghouse Electric Corp
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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
    • 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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  • the method of producing zirconium-base alloys having improved mechanical properties and corrosion resistance comprising heating the alloy to a temperature within the all beta phase region for a period of time to place in solution the alloyingcomponents and impurities while preventing excessive grain growth, quenching the alloy at a rate of at least 90 F. per minute to a temperature below the all alpha phase temperature, reheating the alloy to a temperature within the all alpha phase region, hot working the alloy while in the alpha phase to effect a minimum reduction in cross-sectional area of at least 40 percent to final size, annealing the alloy at a temperature within the alpha phase, and thereafter cooling the alloy to room temperature.
  • zirconium has two important drawbacks; namely, low strength and highly variable corrosion behavior for use in nuclear reactors.
  • the low neutron capture cross section of zirconium makes it an attractive material for nuclear reactors.
  • zirconium base alloys have been developed which display enhanced physical and mechanical properties as well as acceptable corrosion resistance when used in high-pressure water, steam or other types of nuclear reactors.
  • Zircaloy is a generic designation for zirconium base alloys that are useful in the nuclear industry due to their low neutron capture cross section, good mechanical properties, high heat resistance, and corrosion resistance. Because of their low neutron absorption, zirconium base alloys such as zircaloy are useful as structural materials and fuel element cladding.
  • U.S. Pat. No. 2,772,964 discloses zircaloy.
  • Zircaloy is available as zircaloy-2 and zircaloy-4, which have compositions of l to 2 percent tin, 0.07 to 0.24 percent iron, 0.05 to 0.15 percent chromium, 0.007 to 0.08 percent nickel, and the balance is zirconium.
  • the nominal composition of zircaloy-4 is 1.5 percent tin, 0.21 percent iron, 0.10 percent chromium, less than 0.007 percent nickel, and the balance being zirconium with incidental impurities.
  • zircaloy is superior in most respects to commercially pure zirconium for reactor purposes, it is desirable to improve the mechanical properties and corrosion resistance of the alloys in order to enable operation of a reactor at higher temperatures and for longer periods of time between refuel-
  • a prior method of working the alloy for use in a reactor consisted of heating a billet to about 1,850 F., forging and/or hot rolling to an intermediate size at temperatures down to 1,650 F., surface conditioning the alloy body at room temperature, reheating to l,650 F., final forging and/or rolling to final size at about 1,550" F., and annealing the end product at about l,550 F. It has been found that superior mechanical properties and corrosion resistance may be obtained by subjecting the alloy to a beta quench, forging and/or rolling in the alpha condition and a modified annealing procedure during working of the alloy from the ingot stage to the final product.
  • FlG. l is a phase diagram of a zirconium-tin binary system
  • FIG. 2 is a graph depicting the heat treating and hot working cycle according to this invention.
  • This invention is particularly directed to processes capable of developing a ductile, high-strength zirconium base alloy having improved corrosion resistance when subjected to elevated temperatures in a steam or water atmosphere such as in a nuclear reactor.
  • the description of the process of this invention is particularly directed to zircaloy, and in particular, zircaloy-2 and zircaloy-4 alloys containing about 1.4 percent tin, but is exemplary of application of the process to zirconium base alloys generally. Changes in the tin content merely shift the limits of the two phase field as well as the magnitude of the alpha and beta phases in which the heat treatment and hot working are performed. For an alloy containing about 1.4 percent tin the upper alpha formation temperature is 1,650 F. and the lower beta formation temperature is 1,630 F.
  • the invention consists of a method for working and heat treating zirconium base alloys including the steps, which are graphically illustrated in FIG. 2, of (A) heating an ingot of the alloy to a temperature of l,778:t50 F. until the center of the ingot reaches this temperature, (B) forging the ingot down to billet (or bar or plate) size such as about 1.25 to 2 inches in one transverse dimension, (C) reheating the billet to a temperature of l,990: :50 F. for 2 to 4 hours or until the center of the billet reaches a minimum of l,940 so that it is in the beta condition, (D) quenching the billet in the beta condition in water at a rate of F.
  • zirconium base alloys both zircaloy-2 and zircaloy-4, which are to be fabricated to a finished size of 0.75 inch or larger.
  • An ingot of the alloy of a diameter of about 16 inches has a length of from about 4 to 7 (feet which is sufficient to provide an ingot weighing from 2,000 to 3,500 pounds.
  • the term ingot refers to any cast member to be subjected to working to reduce it to desired size and shape.
  • surface temperatures are determined by optical pyrometers or thermocouples are employed, and when temperatures are indicated without qualification as to their location the surface temperatures are meant. Initially, the ingot is heated to a temperature of 1,7783'50" F.
  • the ingot is then initially forged at this temperature without being allowed to cool below about l,400 F., down to a billet or plate size of about 7 inches minimum thickness which size is dictated by the maximum billet size acceptable by a rolling mill for a subsequent rolling operation.
  • the billet may then be cut to convenient lengths.
  • the purpose of the initial heating operation at about 1,778 F. is to permit alloying elements and impurities to go into solution in the zirconium in order to improve the subsequent hot working or forging operation.
  • the ingot is held at this temperature for a sufficient time but not exceeding 30 minutes at temperature to prevent excessive grain growth.
  • the amount of the hot working or forging following the initial heating is dictated in part by the size of the rolling mill in which the billet is to be subsequently rolled after the beta quench D.
  • the amount of the initial hot work or forging is controlled by the amount of reduction after the beta quench. That is, after the beta quench, the billet must be reduced by hot working or forging by an amount greater than 40 percent in order to obtain the desired final properties.
  • the billet cools to a temperature below l,400 F. before the desired billet size is obtained, the billet is reheated (B one or more times to about l,500 F. and hot working or forging (B is continued until the desired billet size is obtained.
  • the primary function of the hot working or forging is to reduce the size of the ingot. During the operation, the grains are broken up. Due to the temperature drop, the alloying elements and impurities come out of solution at the grain boundaries.
  • the resulting billet is reheated (C) into the beta phase until the entire billet is at a temperature of l,990* -J0 F.
  • the billet is soaked at temperature for a sufficient time for the center of thebillet to reach a minimum of l,940 F. or for from 2 to 4 hours for the purpose of dissolving all alloying elements and impurities to produce a solid solution thereof. If the ingot is held at temperature for periods substantially longer than about 4 hours, there is excessive grain growth.
  • the billet is quenched (D) in water at a quenching rate of at least 90 F. per minute to a temperature below the alpha and alpha plus beta transformation; temperatures in order to retain the alloying elements and impurities in solution and to minimize grain growth.
  • the water is preferably at room temperature and the minimum ratio of water to metal ranges from 15:1 to 25:1.
  • each billet After quenching to room temperature it is necessary to surface condition each billet, as by scarfing, to remove defects such as rolled-in oxides (ZrO to obtain optimum corrosion resistance.
  • ZrO rolled-in oxides
  • Such oxides develop when heated in ordinary furnace atmospheres, but may be avoided when controlled reducing atmospheres are used. Under the latter heating conditions, however, surface oxides are formed when the billet is quenched in water. If the alloy is to be used under circumstances where surface perfection and corrosion resistance is not of paramount importance, the alloy billet may be quenched down to a temperature of about 1,450 F. and then hot worked to final size as by step G.
  • the billet is then reheated (F) to a temperature of 1,450i5 0 F. for a time long enough for the center of the billet to reach a minimum of 1,400 F. and preferably about l,450 F. At those temperatures, the billet is within the alpha phase where good metal working properties are obtained without cracking during subsequent hot rolling or forging. During this stage there is a minimum of precipitation of the alloying elements and impurities at these temperatures.
  • Another advantage of heating into the alpha-phase without going into the upper beta range is to obtain satisfactory metal working properties without growth into excessive grain sizes which develop at the higher alpha plus beta and beta-phase temperatures.
  • this hot workingor forging step G there must be a minimum of 40 percent reduction in size in order to break up the larger grain structures and to impart desirable physical properties including improved elongation.
  • the prior heating step F was performed within the alpha-phase, the initial heating of the ingot at step A occurred in the beta-phase for which reason prior beta structure or large grains may have developed and persisted during the subsequent hot working step B and the quenching step D. For that reason, a reduction of at least 40 percent in size of the billet is necessary to achieve improved elongation by breaking up the larger grains.
  • a typical grain size is ASTM 2 to and a preferred grain size of 5 to 8.
  • the billet is reheated (G1) one or more times to about l,450 F. for additional working or forging
  • the billet is annealed (H) at 1,450i50 F. for to 30 minutes or for a sufiicient time to relieve stresses induced during the prior forging or rolling operation of step G.
  • the annealing also provides for an equiaxed small grain structure which is conductive to high corrosion resistance.
  • the alloy is then air cooled (l) to room temperature and the alloy member is ready for use as by machining, cold working, fabrication, welding or the like.
  • this process provides an alloy material having improved ductility and tensile properties.
  • beta quench and alpha hot working technique of this invention provide greatly improved corrosion resistance properties.
  • Test results for the corrosion rate of zircaloy test coupons prepared by the beta quench and alpha hot working technique are shown in table ll. Comparison of the quenched and rolled zircaloy is made with published standard resultsfor corrosion tests.
  • weight gains are measured in milligrams per square decimeter (mg./dm.
  • the maximum weight gain under this test tolerated for zircaloy used in a nuclear reactor is 38 mg./dm. in addition, by visual appearance, the zircaloy surface must have a continuous, black, adherent corrosion film with no corrosion film deflects.
  • the zircaloy as beta quenched and alpha rolled meets the requirements of weight gain and visual appearance for use in a nuclear reactor.
  • the method off producing zirconium-base alloys having improved mechanical properties and corrosion resistance, the steps comprising heating the alloy to a temperature within the all beta phase region for a period of time to place in solution the alloying components and impurities while preventing excessive grain growth, quenching the alloy at a rate of at least 90 F. per minute to a temperature below the all alpha phase temperature, reheating the alloy to a temperature within the all alpha phase region, hot working the alloy while in the alpha phase to effect a minimum reduction in cross sectional area of at least 40 percent to final size, annealing the alloy at a temperature within the alpha phase, and thereafter cooling the alloy to room temperature.
  • the alloys have a composition consisting essentially of, by weight, from 1.0 percent to 2.0 percent tin, from 0.05 percent to 0.25 percent iron, from 0.05 percent to 0.15 percent chromium, from 0.007 percent to 0.08 percent nickel, and the balance essentially zirconium with incidental impurities, and the alloy is heated to a temperature ranging from l,950 to 2,050 F., quenching the alloy to a temperature below the all alpha phase at a minimum quenching rate of 90 F. per minute, hot working the alloy to effect a minimum reduction in the cross-sectional area of 40 percent while at a temperature within the range between l.l50 F. and l,500 F. annealing the alloy within the temperature range of l,400 to l,500 F., and cooling the alloy to room temperature.
  • the method for producing alloys having a composition consisting essentially of, by weight, from 1.0 percent to 2.0 percent tin, from 0.05 percent to 0.25 percent iron, from 0.05 percent to 0.15 percent chromium, from 0.007 percent to 0.08 percent nickel, and the balance essentially zirconium with incidental impurities comprising heating the alloy to a temperature ranging from l,725 to l,825 F., hot working the alloy above a temperature of about l,400 F., reheating the alloy to a temperature ranging from 1,950 to 2,050 F. for 2 to 4 hours, quenching the alloy to a maximum temperature below the alpha and the alpha plus beta range at a minimum quenching rate of F.

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US515297A 1965-12-17 1965-12-17 Method for producing wrought zirconium alloys Expired - Lifetime US3645800A (en)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865635A (en) * 1972-09-05 1975-02-11 Sandvik Ab Method of making tubes and similar products of a zirconium alloy
US4000013A (en) * 1974-07-12 1976-12-28 Atomic Energy Of Canada Limited Method of treating ZR-Base alloys to improve post irradiation ductility
US4094706A (en) * 1973-05-11 1978-06-13 Atomic Energy Of Canada Limited Preparation of zirconium alloys
DE2903476A1 (de) * 1978-01-30 1979-08-02 Teledyne Ind Verfahren zur verringerung der haeufigkeit von legierungs- und verunreinigungsausscheidungen in zirkoniumlegierungen
US4219372A (en) * 1978-12-19 1980-08-26 Teledyne Industries, Inc. Homogenization of zirconium alloys
EP0085553A2 (en) * 1982-01-29 1983-08-10 Westinghouse Electric Corporation Zirconium alloy fabrication processes
US4584030A (en) * 1982-01-29 1986-04-22 Westinghouse Electric Corp. Zirconium alloy products and fabrication processes
DE3609074A1 (de) * 1985-03-19 1986-10-02 Compagnie Européenne du Zirconium Cezus, Courbevoie Verfahren zum herstellen von komposit-huellrohren fuer kernbrennstoffe sowie danach erhaltene produkte
US4647317A (en) * 1984-08-01 1987-03-03 The United States Of America As Represented By The Department Of Energy Manufacturing process to reduce large grain growth in zirconium alloys
US4649023A (en) * 1985-01-22 1987-03-10 Westinghouse Electric Corp. Process for fabricating a zirconium-niobium alloy and articles resulting therefrom
US4664727A (en) * 1982-06-21 1987-05-12 Hitachi, Ltd. Zirconium alloy having superior corrosion resistance
US4678521A (en) * 1981-07-29 1987-07-07 Hitachi, Ltd. Process for producing zirconium-based alloy and the product thereof
US4775428A (en) * 1986-05-21 1988-10-04 Compagnie Europeenne Du Zirconium Cezus Production of a strip of zircaloy 2 or zircaloy 4 in partially recrystallized state
US4908071A (en) * 1985-03-12 1990-03-13 Santrade Limited Method of manufacturing tubes of zirconium alloys with improved corrosion resistance for thermal nuclear reactors
EP0895247A1 (en) * 1997-08-01 1999-02-03 Siemens Power Corporation Method of manufacturing zirconium niobium tin alloys for nuclear fuel rods and structural parts for high burnup
US6126762A (en) * 1998-03-30 2000-10-03 General Electric Company Protective coarsening anneal for zirconium alloys
FR2849865A1 (fr) * 2003-01-13 2004-07-16 Cezus Co Europ Zirconium Procede de fabrication d'un demi-produit en alliage de zirconium pour l'elaboration d'un produit plat et utilisation

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
US3097094A (en) * 1960-09-06 1963-07-09 Westinghouse Electric Corp Zirconium alloys
US3121034A (en) * 1962-03-13 1964-02-11 Anderko Kurt Zirconium alloy treatment process
US3287111A (en) * 1965-10-14 1966-11-22 Harold H Klepfer Zirconium base nuclear reactor alloy

Patent 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
US3097094A (en) * 1960-09-06 1963-07-09 Westinghouse Electric Corp Zirconium alloys
US3121034A (en) * 1962-03-13 1964-02-11 Anderko Kurt Zirconium alloy treatment process
US3287111A (en) * 1965-10-14 1966-11-22 Harold H Klepfer Zirconium base nuclear reactor alloy

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865635A (en) * 1972-09-05 1975-02-11 Sandvik Ab Method of making tubes and similar products of a zirconium alloy
US4094706A (en) * 1973-05-11 1978-06-13 Atomic Energy Of Canada Limited Preparation of zirconium alloys
US4000013A (en) * 1974-07-12 1976-12-28 Atomic Energy Of Canada Limited Method of treating ZR-Base alloys to improve post irradiation ductility
DE2903476A1 (de) * 1978-01-30 1979-08-02 Teledyne Ind Verfahren zur verringerung der haeufigkeit von legierungs- und verunreinigungsausscheidungen in zirkoniumlegierungen
US4219372A (en) * 1978-12-19 1980-08-26 Teledyne Industries, Inc. Homogenization of zirconium alloys
US4678521A (en) * 1981-07-29 1987-07-07 Hitachi, Ltd. Process for producing zirconium-based alloy and the product thereof
EP0085553A2 (en) * 1982-01-29 1983-08-10 Westinghouse Electric Corporation Zirconium alloy fabrication processes
US4584030A (en) * 1982-01-29 1986-04-22 Westinghouse Electric Corp. Zirconium alloy products and fabrication processes
EP0085553B1 (en) * 1982-01-29 1988-11-23 Westinghouse Electric Corporation Zirconium alloy fabrication processes
US4664727A (en) * 1982-06-21 1987-05-12 Hitachi, Ltd. Zirconium alloy having superior corrosion resistance
US4647317A (en) * 1984-08-01 1987-03-03 The United States Of America As Represented By The Department Of Energy Manufacturing process to reduce large grain growth in zirconium alloys
US4649023A (en) * 1985-01-22 1987-03-10 Westinghouse Electric Corp. Process for fabricating a zirconium-niobium alloy and articles resulting therefrom
US4908071A (en) * 1985-03-12 1990-03-13 Santrade Limited Method of manufacturing tubes of zirconium alloys with improved corrosion resistance for thermal nuclear reactors
DE3609074A1 (de) * 1985-03-19 1986-10-02 Compagnie Européenne du Zirconium Cezus, Courbevoie Verfahren zum herstellen von komposit-huellrohren fuer kernbrennstoffe sowie danach erhaltene produkte
US4775428A (en) * 1986-05-21 1988-10-04 Compagnie Europeenne Du Zirconium Cezus Production of a strip of zircaloy 2 or zircaloy 4 in partially recrystallized state
EP0895247A1 (en) * 1997-08-01 1999-02-03 Siemens Power Corporation Method of manufacturing zirconium niobium tin alloys for nuclear fuel rods and structural parts for high burnup
US6126762A (en) * 1998-03-30 2000-10-03 General Electric Company Protective coarsening anneal for zirconium alloys
US6355118B1 (en) 1998-03-30 2002-03-12 General Electric Company Protective coarsening anneal for zirconium alloys
FR2849865A1 (fr) * 2003-01-13 2004-07-16 Cezus Co Europ Zirconium Procede de fabrication d'un demi-produit en alliage de zirconium pour l'elaboration d'un produit plat et utilisation
WO2004072318A1 (fr) * 2003-01-13 2004-08-26 Compagnie Europeenne Du Zirconium-Cezus Procede de fabrication d’un demi-produit en alliage de zirconium pour l’elaboration d’un produit plat et utilisation
US20060081313A1 (en) * 2003-01-13 2006-04-20 Pierre Barberis Method for the production of a semi-finished product made of zirconium alloy for the production of a flat product and use thereof

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