EP0248397B1 - Verfahren zum Herstellen von Zirkon für Schutzhüllen durch Schmelzen von geglühtem Zirkon mit Elektronenstrahlen - Google Patents

Verfahren zum Herstellen von Zirkon für Schutzhüllen durch Schmelzen von geglühtem Zirkon mit Elektronenstrahlen Download PDF

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Publication number
EP0248397B1
EP0248397B1 EP87107946A EP87107946A EP0248397B1 EP 0248397 B1 EP0248397 B1 EP 0248397B1 EP 87107946 A EP87107946 A EP 87107946A EP 87107946 A EP87107946 A EP 87107946A EP 0248397 B1 EP0248397 B1 EP 0248397B1
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EP
European Patent Office
Prior art keywords
sponge
melting
vacuum
zirconium
process according
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.)
Expired - Lifetime
Application number
EP87107946A
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English (en)
French (fr)
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EP0248397A2 (de
EP0248397A3 (en
Inventor
Samuel Austin Worcester
Young Jin Kwon
Charles Robert Woods
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Westinghouse Electric Corp
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Westinghouse Electric Corp
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Publication date
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Publication of EP0248397A3 publication Critical patent/EP0248397A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/22—Remelting metals with heating by wave energy or particle radiation
    • C22B9/228—Remelting metals with heating by wave energy or particle radiation by particle radiation, e.g. electron beams
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/04—Refining by applying a vacuum

Definitions

  • This invention relates to the production of purified zirconium.
  • the conventional process for making zirconium metal utilizes a fluidized bed process in which the ore is subjected to a chlorination step which produces a relatively impure, hafnium-containing zirconium tetrachloride and by-product silicon tetrachloride (which by-product is relatively easily separated).
  • the hafnium and zirconium containing material is then subjected to a number of purifying operations and also a complex hafnium separation operation. These operations result in purified oxides of zirconium and hafnium, which, of course, are maintained separate.
  • the purified oxides are separately chlorinated.
  • Zirconium and hafnium are commonly reduced from the chloride by means of a reducing metal, typically magnesium.
  • U.S. Patent Specification No. 3,966,460 describes a process of introducing zirconium tetrachloride vapor onto molten magnesium, with the zirconium being reduced and traveling down through the magnesium layer to the bottom of the reactor and forming a metallic sponge.
  • the metallic sponge (containing remaining chloride and some remaining excess reducing metal) is then placed in a distillation vessel for removal of the remaining salt and reducing metal by high temperature vacuum distillation.
  • the sponge material is generally crushed, screened and pressed into electrodes for vacuum arc melting. Particularly, the material is multiple (typical double or triple) vacuum arc melted to provide ingots which are then further fabricated into various shapes.
  • Most of the zirconium currently is used to produce Zircaloy.
  • Zircaloy tubes as cladding material to contain the uranium dioxide fuel.
  • a Zircaloy ingot is processed into a so-called "trex" and pilgering operations are used to reduce the trex inside diameter and wall thickness to size.
  • Ultra-pure zirconium has been proposed for a liner for the inside surface of Zircaloy tubing which is used as a cladding for nuclear fuel and is described in, for example, U.S. Patent Specification No. 4,372,817 (Armijo et al.).
  • a similar use of moderate purity material is proposed in U.S. Patent Specification No. 4,200,492 (Armijo et al.).
  • the ultra-pure zirconium material described has been purified by iodide cells to produce so called "crystal bar” material.
  • This rather expensive crystal bar processing is performed after reduction and is described, for example, in U.S. Patent Specification No. 4,368,072 (Siddal).
  • EB (electron beam) melting of materials has been discussed in a number of U.S. patent specifications. EB melting has been used to consolidate crushed particles or chips in so called hearth furnaces and to separate impurities by either overflowing floating inclusions (U.S. Patent Specification No. 4,190,404 (Drs et al.) or to produce an electrode for arc melting (U.S. Patent Specification No. 4,108,644 (Walberg et al.).
  • a number of U.S. patent specifications have used EB melting of powders or granules, often producing an ingot in a chilled mold. These powder melting EB patent specifications include U.S. Patent Specification Nos.
  • 3,091,525 to (D. A. Hunt) describes adding a small amount of zirconium, for example, to hafnium, for example and melting in an EB furnace to deoxidize the hafnium.
  • Japanese application 1979-144789 Kawakita published as patent publication 1981-67788 describes the use of a very small ingot with a high power density and ultra slow melting to produce a deep molten pool to produce a high purity ingot directly usable for lining of Zircaloy tubing for nuclear reactor applications.
  • Such laboratory sized apparatus with its high powered consumption and very low throughput is, of course, not practical for commercial production.
  • a process for producing zirconium in purified form comprises reducing zirconium tetrachloride to produce a sponge of metallic zirconium which is distilled to generally remove residual magnesium and residual magnesium chloride, and melting the distilled sponge to produce an ingot, characterized by vacuum baking the distilled sponge for at least one-half hour at 120-400°C; and electron beam melting said vacuum baked sponge.
  • this process provides material much purer than the so-called sponge material and almost as good as the crystal bar material, at a fraction of the cost of crystal bar material.
  • Generally purified zirconium produced according to the present invention has oxygen in the 250-350 ppm range and iron in the 50-300 ppm range.
  • Total impurities are generally in the 500-1000 ppm range (total impurities for these purposes generally comprise the elements listed in the afore-mentioned U.S. Patent Specification No. 4,200,492).
  • Vacuum baking in the temperature range of 120-400°C generally removes moisture absorbed on the surface of the sponge (it is felt that the moisture generally is in the form of absorbed moisture on small amounts of residual magnesium chloride salt which still may remain after distillation).
  • the EB melting generally removes iron from the zirconium. The combined baked and EB melted material provides high purity material approaching the quality of crystal bar.
  • the vacuum baked material is generally maintained in an inert atmosphere between the vacuum baking and EB melting to avoid moisture pick up.
  • the vacuum baking can be performed within the EB furnace prior to the start of melting and the vacuum maintained until melting is begun, thus generally avoiding the regaining of moisture.
  • the distilled sponge is tested and only sponge having less than about 600 ppm of oxygen is selected for use in the instant process.
  • the iron impurity level is reduced by about a factor of 2 on each pass through the EB furnace (that is, when the intermediate ingot form during the first EB melting pass is used as the consumable electrode for a second EB melting, the iron level is reduced by another factor of approximately 2).
  • this process makes the speed of the first EB melting less critical, and provides for a more controlled and more complete moisture removal, and thus a lower oxygen content product for a given oxygen level in the distilled sponge.
  • this process gives oxygen levels in the 250-350 ppm range (which, of course, are preferred in any event, but are much more controllably obtained in the instant invention).
  • These two inventions are desirably combinable such that the material can be prebaked, EB melted, and then vacuum arc melted for optimum properties.
  • the baking at 120-400°C for at least one-half hour is most desirably done within the EB furnace such that the material can be maintained under vacuum until melting
  • the material can be baked in any vacuum chamber, including the EB welding chambers which are sometimes used to weld end stubs on electrodes which have been fabricated by pressing sponge material.
  • the crushed sponge can be baked prior to pressing (again preferably generally keeping the material in a dry, inert atmosphere) and then pressed and possibly subjected to a second baking cycle.
  • the product of this process has low total impurities, and especially a low oxygen and low iron (the iron level generally being controlled by the number of passes through the EB furnace).
  • the process is relatively inexpensive and, being compatible with existing production processes, requires little additional capital investment.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Claims (8)

  1. Ein Verfahren zur Herstellung von Zirkon in gereinigter Form, welches Verfahren Reduzieren von Zirkon-Tetrachlorid zur Erzeugung eines Schwammes aus metallischem Zirkon, welches destilliert wird, um allgemein Restmagnesium und Restmagnesium-Chlorid zu entfernen, und Schmelzen des destilierten Schwammes zur Erzeugung eines Barrens umfaßt, gekennzeichnet durch Backen des destilierten Schwammes für zumindest eine halbe Stunde bei einer Temperatur von 120° bis 400° C im Vakuum; und Schmelzen des im Vakuum gebackenen Schwammes mittels eines Elektronenstrahls.
  2. Ein Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der im Vakuum gebackene Schwamm zwischen dem Vakuumbacken und dem Elektronenstrahlschmelzen im wesentlichen in einer inerten Atmosphäre gehalten wird.
  3. Ein Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Vakuumbacken in einem Elektronenstrahlofen vor dem Schmelzen durchgeführt wird, und daß das Elektronenstrahlschmelzen dann ohne Unterbrechung des Vakuums durchgeführt wird.
  4. Ein Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß ein Drehzufuhrelektronenstrahlofen verwendet wird und daß der Schwamm geschmolzen wird, ohne daß er in eine Elektrode konsolidiert wird.
  5. Ein Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß der mittels Elektronenstrahlofen mehrfach verschwenkte Strahlen besitzt.
  6. Ein Verfahren nach Anspruch 3, 4 oder 5, dadurch gekennzeichnet, daß der Elektronenstrahl geschmolzene Schwamm mittels Vielfachdurchgängen durch einen Vakuumlichtbogen geschmolzen wird.
  7. Ein Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der im Vakuum gebackene Schwamm der Atmosphäre für weniger als eine Stunde zwischen dem Vakuumbacken und dem Elektronenstrahlschmelzen ausgesetzt wird.
  8. Ein Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der destillierte Schwamm getestet wird und daß Schwamm mit 600 ppm oder mehr Sauerstoff zurückgewiesen wird.
EP87107946A 1986-06-05 1987-06-02 Verfahren zum Herstellen von Zirkon für Schutzhüllen durch Schmelzen von geglühtem Zirkon mit Elektronenstrahlen Expired - Lifetime EP0248397B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US87118286A 1986-06-05 1986-06-05
US871182 1986-06-05

Publications (3)

Publication Number Publication Date
EP0248397A2 EP0248397A2 (de) 1987-12-09
EP0248397A3 EP0248397A3 (en) 1990-05-02
EP0248397B1 true EP0248397B1 (de) 1992-08-19

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP87107946A Expired - Lifetime EP0248397B1 (de) 1986-06-05 1987-06-02 Verfahren zum Herstellen von Zirkon für Schutzhüllen durch Schmelzen von geglühtem Zirkon mit Elektronenstrahlen

Country Status (4)

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EP (1) EP0248397B1 (de)
KR (1) KR880000612A (de)
DE (1) DE3781206T2 (de)
ES (1) ES2033736T3 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849016A (en) * 1987-12-18 1989-07-18 Westinghouse Electric Corp. Combined ultra slow electron beam and vacuum arc melting for barrier tube shell material
US5062887A (en) * 1991-02-08 1991-11-05 Westinghouse Electric Corp. Process for chloride removal from sponge metal
DE60130477T2 (de) * 2000-10-02 2008-01-03 Nippon Mining & Metals Co., Ltd. Hochreines Zirkonium oder Hafnium, diese beinhaltendes Sputtering Target und mit diesesm hergestellte dünnen Filme, Verfahren zur Herstellung von hochreinem Zirkonium oder Hafnium und Herstellungsverfahren für Pulver aus hochreinem Zirkonium oder Hafnium
US9938605B1 (en) 2014-10-01 2018-04-10 Materion Corporation Methods for making zirconium based alloys and bulk metallic glasses
CN119640056A (zh) * 2024-12-25 2025-03-18 攀钢集团攀枝花钢铁研究院有限公司 一种高纯海绵钒的制备及纯化方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2814560A (en) * 1954-04-23 1957-11-26 James S Ballantine Apparatus and process for melting material of high melting point
BE568331A (de) * 1956-07-27 1900-01-01
NL239776A (de) * 1958-08-04
DE1110877B (de) * 1959-04-24 1961-07-13 Heraeus Gmbh W C Verfahren zum Erschmelzen von Metallbloecken mittels Elektronenstrahlen
US3966460A (en) * 1974-09-06 1976-06-29 Amax Specialty Metal Corporation Reduction of metal halides
US4190404A (en) * 1977-12-14 1980-02-26 United Technologies Corporation Method and apparatus for removing inclusion contaminants from metals and alloys

Also Published As

Publication number Publication date
EP0248397A2 (de) 1987-12-09
DE3781206D1 (de) 1992-09-24
ES2033736T3 (es) 1993-04-01
DE3781206T2 (de) 1993-02-18
EP0248397A3 (en) 1990-05-02
KR880000612A (ko) 1988-03-28

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