US3664825A - Method for manufacturing zirconium alloys and alloys manufactured according to the method - Google Patents

Method for manufacturing zirconium alloys and alloys manufactured according to the method Download PDF

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Publication number
US3664825A
US3664825A US10042A US3664825DA US3664825A US 3664825 A US3664825 A US 3664825A US 10042 A US10042 A US 10042A US 3664825D A US3664825D A US 3664825DA US 3664825 A US3664825 A US 3664825A
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United States
Prior art keywords
alloy
zirconium
phase
weight
alloys
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Expired - Lifetime
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US10042A
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English (en)
Inventor
Mats Soren Bergqvist
Olof Krister Kallstrom
Nils Axel Gunnar Okvist
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Santrade Ltd
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Sandvikens Jernverks AB
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Assigned to SANTRADE LTD., A CORP. OF SWITZERLAND reassignment SANTRADE LTD., A CORP. OF SWITZERLAND ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: SANDVIK AKTIEBOLAG, A CORP. OF SWEDEN
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Classifications

    • 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

  • This object is met by including, amongst the components when the alloy is manufactured by melting, one or more metallic carbides the metallic carbide so added being in such an amount that the final carbon content of the alloy is 1'403 00 parts of weight per million parts of Weight of the alloy.
  • the present invention relates to a method of making zirconium alloys of the known type which essentially contain, besides zirconium and an insignificant amount of impurities, from about 0.2 to about 2.5 weight percent tin and in toto from 0.1 to 3.0 weight percent of one or more of the elements iron, chromium, nickel and niobium, whereby to give the alloys a higher than conventional ductility and improved surface properties.
  • Alloys of this kind known as Zircaloy 2 and Zircaloy 4 respectively, which besides tin contain small quantities of iron, chromium and nickel, or iron and chromium, respectively, have been found especially suitable for use in canning tubes (tubes de gaine) for atomic reactors because of their good strength, and also their corrosion resistance at higher temperatures, and their small crosssection for absorption of neutrons.
  • each ,H-crystal is penetrated by groups of substantially parallel discs of a-phase. It is probable that the points of nucleation for the u-phase discs in the main have been situated in the grain boundaries of the B-crystals, which circumstance has resulted in that adjacent nuclei in such a grain boundary have had very similar conditions for their formation, resulting in a growth of similarly orientated discs.
  • the structure thus formed is, in the following, called A-structure.
  • nuclei can be caused within the fi-crystals.
  • the points of nucleation are "ice then situated adjacent to particles in the crystals.
  • the nuclei of several a-phase discs are formed, which discs then grow in different directions.
  • Discs which have grown from different nucleating particles will cross each other, resulting in that the structure looks like a plaited network, often referred to as basket weave structure.
  • This structure is, in the following, called B-structure.
  • the B-structure is, in several respects, more advantageous than the earlier mentioned A-structure, i.a. with regard to the ductility and surface property of the ma terial.
  • the B-structure is superior to the A-structure with regard to ductility.
  • a portion of the canning tube adjacent the brazing joint undergoes the phase transformation a-pI-u. If the transformation fl-a gives A-structure, the ductility becomes substantially reduced in comparison with a situation in which the transformation gives B-structure.
  • the desired B-structure can be obtained in the said phase transformation by adding a suitable amount of a metallic carbide when melting together the components of the alloy.
  • the relative amount of the added metallic carbide should be carefully controlled, so that the final alloy has a final carbon content of at least 140, and preferably 150, and at the most 300 parts by weight per million parts by weight of the alloy (140-300 p.p.m.).
  • the addition may normally consist of zirconium carbide, but it is possible to replace the zirconium carbide partially or totally by one or more metallic carbides such as iron, chromium and niobium carbides.
  • the addition of zirconium carbide and/or other metallic carbide ought to be of such a size order that the final carbon content of the alloy does not exceed 400 and preferably amounts to 140-300 parts by weight per million parts by weight of the eventually alloy. If the carbon content is below the aforesaid lower limit, 140 p.p.m., the desired B-structure is not obtained. If, on the other hand, the upper limit 300 is exceeded, the corrosion resistance is impaired.
  • the metallic carbide addition preferably should be in the form of a powder in order to obtain the favorable result according to the invention.
  • zirconium easily forms oxides and absorbs atmospheric and other impurities at raised temperatures, the constituents of the alloy should be melted in vacuum in an arc furnace.
  • the melting is as a rule started with zirconium sponge and Zirconium scrap, desired quantities of the other alloying elements being added.
  • zirconium constituents in total per million parts by weight do not contain more carbon than 100 parts and preferably not more than parts by weight.
  • zirconium carbide, and/or other metal carbides in such a quantity that the final alloy obtains the carbon content earlier referred to.
  • the raw materials shall be as pure as possible but often it cannot be avoided that insignificant amounts of impurities, among them carbon, may occur therein.
  • these impurities be held to a low amount, and that at least 50%, and preferably at least 80%, of the carbon of the final alloy be carbon which has been supplied by the additions of zirconium carbide and/or other metal carbides.
  • zirconium carbide and/or other metal carbides it can be mentioned that in certain cases insignificant amounts of oxygen and/or silicon may be present in the alloy as an active constituent.
  • the invention will now be illustrated by an example relating to the manufacture of Zircaloy 2, containing in percent by weight 1.4% tin, 0.12% iron, 0.10% chromium, 0.06% nickel and the remainder zirconium with insignificant amounts of impurities.
  • the initial materials for the melting which was performed in an arc furnace under vacuum, were zirconium sponge, zirconium scrap and desired minor quantities of the other alloy constituents.
  • the carbon content in the initial material was about 0.005 percent of weight.
  • Zircaloy 4 containing in percent by weight 1.5% tin, 0.21% iron, 0.12% chromium and the remainder zirconium with insignificant amount of impurities was produced by melting in an arc furnace under vacuum a material which except for an addition of 0.12% by weight of chromium carbide was practically free from carbon. After hot working in the fi-range the alloy had a smooth surface, while an alloy of the above kind produced in a conventional way had an irregular and rough surface.
  • the final carbon content was between 150 and 300 parts by Weight per million parts by weight of the total alloy.

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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)
  • Powder Metallurgy (AREA)
US10042A 1969-02-21 1970-02-09 Method for manufacturing zirconium alloys and alloys manufactured according to the method Expired - Lifetime US3664825A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
SE2402/69A SE323525B (enrdf_load_stackoverflow) 1969-02-21 1969-02-21

Publications (1)

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US3664825A true US3664825A (en) 1972-05-23

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US10042A Expired - Lifetime US3664825A (en) 1969-02-21 1970-02-09 Method for manufacturing zirconium alloys and alloys manufactured according to the method

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US (1) US3664825A (enrdf_load_stackoverflow)
JP (1) JPS5020938B1 (enrdf_load_stackoverflow)
DE (1) DE2008320C3 (enrdf_load_stackoverflow)
FR (1) FR2035397A5 (enrdf_load_stackoverflow)
GB (1) GB1252238A (enrdf_load_stackoverflow)
NO (1) NO122041B (enrdf_load_stackoverflow)
SE (1) SE323525B (enrdf_load_stackoverflow)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108687A (en) * 1975-12-12 1978-08-22 Ugine Aciers Process for improving the heat resistance of zirconium and its alloys
US4164420A (en) * 1977-01-07 1979-08-14 Ugine Aciers Master alloy for the preparation of zirconium alloys
US4212686A (en) * 1978-03-03 1980-07-15 Ab Atomenergi Zirconium alloys
US4279667A (en) * 1978-12-22 1981-07-21 General Electric Company Zirconium alloys having an integral β-quenched corrosion-resistant surface region
US4360389A (en) * 1975-11-17 1982-11-23 General Electric Company Zirconium alloy heat treatment process
US4724016A (en) * 1985-09-19 1988-02-09 Combustion Engineering, Inc. Ion-implantation of zirconium and its alloys
US4986957A (en) * 1989-05-25 1991-01-22 General Electric Company Corrosion resistant zirconium alloys containing copper, nickel and iron
US5073336A (en) * 1989-05-25 1991-12-17 General Electric Company Corrosion resistant zirconium alloys containing copper, nickel and iron
US5539791A (en) * 1992-02-28 1996-07-23 Siemens Aktiengesellschaft Material and structural part made from modified zircaloy
CN114807679A (zh) * 2022-04-29 2022-07-29 西部新锆核材料科技有限公司 一种锆或锆合金残料锭高效熔炼方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52102238U (enrdf_load_stackoverflow) * 1976-01-30 1977-08-03
EP0287888B1 (en) * 1987-04-23 1991-05-02 General Electric Company Corrosion resistant zirconium alloys
DE3873643T2 (de) * 1987-06-23 1993-03-25 Commissariat Energie Atomique Verfahren zur herstellung eines rohres auf zirconiumlegierungsbasis fuer kernkraftreaktoren und verwendung.

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4360389A (en) * 1975-11-17 1982-11-23 General Electric Company Zirconium alloy heat treatment process
US4108687A (en) * 1975-12-12 1978-08-22 Ugine Aciers Process for improving the heat resistance of zirconium and its alloys
US4164420A (en) * 1977-01-07 1979-08-14 Ugine Aciers Master alloy for the preparation of zirconium alloys
US4212686A (en) * 1978-03-03 1980-07-15 Ab Atomenergi Zirconium alloys
US4279667A (en) * 1978-12-22 1981-07-21 General Electric Company Zirconium alloys having an integral β-quenched corrosion-resistant surface region
US4724016A (en) * 1985-09-19 1988-02-09 Combustion Engineering, Inc. Ion-implantation of zirconium and its alloys
US4986957A (en) * 1989-05-25 1991-01-22 General Electric Company Corrosion resistant zirconium alloys containing copper, nickel and iron
US5073336A (en) * 1989-05-25 1991-12-17 General Electric Company Corrosion resistant zirconium alloys containing copper, nickel and iron
US5539791A (en) * 1992-02-28 1996-07-23 Siemens Aktiengesellschaft Material and structural part made from modified zircaloy
CN114807679A (zh) * 2022-04-29 2022-07-29 西部新锆核材料科技有限公司 一种锆或锆合金残料锭高效熔炼方法

Also Published As

Publication number Publication date
DE2008320C3 (de) 1973-11-15
GB1252238A (enrdf_load_stackoverflow) 1971-11-03
FR2035397A5 (enrdf_load_stackoverflow) 1970-12-18
DE2008320B2 (de) 1972-01-27
SE323525B (enrdf_load_stackoverflow) 1970-05-04
JPS5020938B1 (enrdf_load_stackoverflow) 1975-07-18
DE2008320A1 (de) 1970-09-10
NO122041B (enrdf_load_stackoverflow) 1971-05-10

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Owner name: SANTRADE LTD., ALPENQUAI 12, CH-6002, LUCERNE, SWI

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:SANDVIK AKTIEBOLAG, A CORP. OF SWEDEN;REEL/FRAME:004085/0132

Effective date: 19820908