EP0134162A1 - Neodymlegierungen und Verfahren zur Herstellung derselben - Google Patents

Neodymlegierungen und Verfahren zur Herstellung derselben Download PDF

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Publication number
EP0134162A1
EP0134162A1 EP84401307A EP84401307A EP0134162A1 EP 0134162 A1 EP0134162 A1 EP 0134162A1 EP 84401307 A EP84401307 A EP 84401307A EP 84401307 A EP84401307 A EP 84401307A EP 0134162 A1 EP0134162 A1 EP 0134162A1
Authority
EP
European Patent Office
Prior art keywords
neodymium
metal
calcium
halide
iron
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.)
Granted
Application number
EP84401307A
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English (en)
French (fr)
Other versions
EP0134162B1 (de
Inventor
Françoise Seon
Bernard Boudot
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Specialites Chimiques
Rhone Poulenc Chimie SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from FR8311139A external-priority patent/FR2548687B1/fr
Application filed by Rhone Poulenc Specialites Chimiques, Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Specialites Chimiques
Priority to AT84401307T priority Critical patent/ATE45989T1/de
Publication of EP0134162A1 publication Critical patent/EP0134162A1/de
Application granted granted Critical
Publication of EP0134162B1 publication Critical patent/EP0134162B1/de
Expired legal-status Critical Current

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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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • 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
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00

Definitions

  • the present invention relates to neodymium alloys and their manufacturing process.
  • ceric rare earth metals which includes lanthanum, cerium, praseodymium and neodymium
  • the latter is the only metal that cannot be manufactured industrially by the electrolysis of these salts. Indeed, it is mentioned in the article by T. KURITA (Denki Kagaku, 1967, 35 (7) p.496-501) that yields of 6 to 20% of pure neodymium are obtained by electrolysis in a molten bath - neodymium chloride, potassium chloride ⁇ .
  • One of the objectives of the present invention is to have available new neodymium alloys obtained according to an industrial manufacturing process.
  • the object of the present invention lies in new neodymium alloys characterized by the fact that they contain neodymium and iron.
  • a variant of the present invention resides in neodymium alloys characterized by the fact that they contain neodymium, iron, and at least one metal from another rare earth chosen from the group formed by yttrium, lanthanum, cerium, praseodymium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, lutetium.
  • the rare earth metal involved in said alloys is therefore any metal belonging to the group formed by yttrium and lanthanides, except samarium, europium and ytterbium.
  • metal TR a metal of a rare earth or a mixture of rare earth metals chosen from the group defined above.
  • Another object of the present invention is the process for manufacturing said alloys, characterized in that it consists in reducing a neodymium halide and optionally a halide of a T.R. metal with a reducing metal, in the presence of iron.
  • neodymium halide neodymium fluoride or neodymium chloride or a mixture thereof is used.
  • neodymium fluoride is used.
  • the halide used is of high purity, that is to say free of residual oxide and of oxyhalide and that it be dry: its water content must be less than 5% and preferably less than 2 X.
  • Neodymium fluoride is available in an anhydrous state because it is a low hygroscopic product.
  • neodymium chloride exists in the form of hydrates containing 6 to 7 moles of water per mole of neodymium chloride. It is generally prepared by the reaction of hydrochloric acid and neodymium sesquioxide.
  • this chloride requires a drying step at a temperature between 100 ° C and 500 ° C but preferably between 200 ° C and 250 ° C.
  • This treatment is also suitable for neodymium fluoride.
  • the drying time can vary between 2 and 24 hours.
  • the particle size of the neodymium halide may vary. It is commercially available in powder form, the particle size of which varies from 40 to 150 ⁇ m.
  • the particle size influencing the reduction speed it is recommended that the powder is fine which can cause grinding operation so that the average particle diameter of the neodymium halide is less than 100 ⁇ m. There is no lower diameter limit.
  • metal halide TR a metal fluoride TR, a metal chloride TR or a mixture thereof can be chosen.
  • the fluoride of the metal TR is used.
  • the properties required and the conditions for using the metal halide TR are identical to those of the neodymium halide.
  • the reducing metal used in the process of the invention can be an alkali metal, an alkaline earth metal or a mixture thereof. Mention may be made, as alkali metal, of sodium, lithium or potassium and, as alkaline earth metal, of calcium or magnesium.
  • Calcium or magnesium is preferably used and even more preferably calcium.
  • the reducing metal is used in the form in which it is sold, whether it is in the solid state or in the form of pellets or balls.
  • a preferred variant of the process of the invention consists in adding to the reaction medium calcium chloride or calcium fluoride as the case may be in order to lower the melting point and the density of the slag formed in the reaction so that the alloy formed neodymium-iron separates more easily.
  • the aim being to obtain a CaF 2 -CaCl 2 slag, the addition when the source of neodymium is neodymium fluoride or neodymium chloride, respectively calcium chloride or calcium fluoride. If the neodymium halide is a mixture of fluoride and chloride, a mixture of chloride and calcium fluoride is added in order to obtain a CaF 2 -CaCl 2 mixture having the composition defined later.
  • calcium chloride should be added when using neodymium fluoride and a metal fluoride TR and calcium fluoride when using uses neodymium chloride and a metal chloride TR. If the neodymium halide or the metal TR is a mixture of fluoride and chloride or if the halides of neodymium and the metal TR are of different nature, it is necessary to add a mixture CaF 2 -CaCl 2 in order to have the desired composition.
  • the method of the invention consists in mixing a neodymium halide, optionally a metal halide TR, a reducing metal, iron and optionally a calcium halide in the proportions given below.
  • the quantity of TR metal halide used is calculated according to the composition of the desired alloy. It will preferably be defined so that the metal TR represents from 0 to 50% of the weight of the mixture constituted by neodymium and the metal TR and even more preferably from 0 to 10%.
  • the amount of reducing metal can vary within wide limits. However, it is advantageous to use a quantity sufficient to reduce the neodymium halide and possibly the metal halide TR but it should not be too large if we do not want to find, in a significant way, in the final alloy.
  • the amount of reducing metal is at least equal to the stoichiometric amount or even in slight excess, up to 20% of the stoichiometric amount.
  • the amount of iron is adjusted according to the desired composition of the alloy. It is such that a fusible alloy with neodymium and iron is obtained at the reaction temperature. It is calculated so that iron represents from 5 to 30% of the weight of the alloy obtained.
  • the amount of calcium halide added is adjusted in order to obtain a slag containing from 30 to 70% by weight of calcium chloride and preferably 60 to 70%.
  • the various halides of neodymium, of metal TR and of calcium and the abovementioned metals constitute "a filler" having the desired weight composition.
  • the constituents of this charge can be reacted in any order: by simultaneous mixing of all the constituents or by making premixes, on the one hand, the halides of neodymium, calcium, optionally of metal TR and on the other hand the reducing metal and the iron.
  • the reaction is carried out at a temperature between 800 ° C and 1100 ° C.
  • the upper limit of temperature is not critical and can reach a value as high as 1400 ° C.
  • a temperature between 900 ° C and 1100 ° C is chosen.
  • the reaction is carried out at atmospheric pressure but in an inert gas atmosphere.
  • rare gases including argon. It is desirable to subject the rare gas to a dehydration and deoxygenation treatment carried out according to the usual techniques, for example by passage through a molecular sieve.
  • the inert atmosphere is maintained throughout the reduction.
  • the duration of the reaction depends on the capacity of the apparatus and its ability to rapidly rise in temperature. Generally, once the desired temperature is reached, it is maintained for a variable duration of approximately 30 minutes to 3 hours.
  • a metallic phase consisting of the neodymium-iron alloy on which floats a slag consisting of CaF 2 -CaCl 2 having a density lower than that of the alloy.
  • the alloy can be immediately separated from the slag by hot casting or allowed to cool under an inert gas atmosphere at room temperature (15 to 25 ° C) so that the alloy solidifies and can then be removed from the mold.
  • the yield of neodymium in the alloy expressed relative to the neodymium contained in the halide varies from 80 to 96%.
  • the metallic phase also contains a metal of another rare earth
  • a yield of rare earth metals compared to the rare earth metals contained in the committed halides varying from 75 95%.
  • the reduction is carried out in a crucible placed in a reactor made of a material resistant to hydrofluoric and hydrochloric vapors.
  • refractory steel for example, from steel containing 25 X of chromium and 20 X of nickel but preferably in inconel which is an alloy containing nickel, chromium (20%), iron (5%), molybdenum (8-10%).
  • Said reactor is equipped with a temperature control device (for example thermocouple), an inlet and an outlet for inert gases. It is provided in its upper part with a double envelope in which circulates a coolant.
  • a temperature control device for example thermocouple
  • This reactor is placed in an induction furnace or in an furnace heated by electrical resistances.
  • a crucible in which the temperature control device is immersed is placed at the bottom of the reactor. It must be made of a material resistant to neodymium halides or have a coating resistant to them. Preferably, a tantalum crucible is used.
  • the molten alloy can be cast in molds, for example, cast iron.
  • the proportion of TR metal can represent from 0 to 50% of the weight of the mixture constituted by neodymium and TR metal and, preferably, from 0 to 10%.
  • the alloys obtained according to the present invention are very rich in neodymium since they can contain up to 95%.
  • They can be used as master alloys in particular in the manufacture of permanent magnets.
  • Example 1 an example of the preparation of a neodymium-iron alloy is given (example 1) and two examples of the preparation of a neodymium-praseodymium-iron alloy (examples 2 and 3).
  • a premix is then made containing 382.2 g of calcium chloride in the dry state and 281.4 g of neodymium fluoride having an average particle diameter of 60 ⁇ m.
  • the previously defined load is then ready for use.
  • the calciothermic reduction reaction of neodymium fluoride is carried out in a tantalum crucible of about 1 liter placed at the bottom of an inconel reactor which is equipped with an inlet and an outlet for argon and a thermocouple introduced.
  • a thermometric sheath which is immersed in the reaction medium contained in the crucible: the upper part of the reactor is provided with a double jacket in which cold water circulates (approximately 10 ° C).
  • a temperature rise is carried out at the same time until the temperature fixed at 1100 ° C. is obtained; this temperature being kept constant for another 30 minutes.
  • neodymium-iron alloy 562 g are collected and 188 g of a neodymium-iron alloy are recovered by hot casting in a cast iron ingot mold.
  • the neodymium yield in the alloy expressed relative to the neodymium contained in the neodymium fluoride is 81%.
  • a premix containing 530.8 g of calcium chloride in the dry state and 390.8 g of a mixture containing 96.4 X of neodymium fluoride and 3.6% of praseodymium fluoride is then made: said mixture having an average particle diameter of 60 ⁇ m.
  • the calciothermic reduction reaction of neodymium fluoride and praseodymium fluoride is carried out in a tantalum crucible of about 1 liter placed at the bottom of an inconel reactor which is equipped with an inlet and an outlet for argon and a thermocouple introduced into a thermometric sheath which is immersed in the reaction medium contained in the crucible: the upper part of the reactor is provided with a double jacket in which circulates cold water (approximately 10 ° C.).
  • a temperature rise is carried out at the same time until the temperature fixed at 1100 ° C. is obtained; this temperature being kept constant for another 30 minutes.
  • 717.2 g of slag are collected and 296 g of a neodymium-praseodymium-iron alloy are recovered by hot casting in a cast iron ingot mold.
  • the yield of rare earths in the alloy expressed relative to the rare earths contained in neodymium and praseodymium fluorides is 90%.
  • Example 2 is reproduced, except that a mixture of neodymium fluoride and praseodymium fluoride is used, but a mixture containing 58% of neodymium chloride and 42% of praseodymium chloride.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP84401307A 1983-07-05 1984-06-22 Neodymlegierungen und Verfahren zur Herstellung derselben Expired EP0134162B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84401307T ATE45989T1 (de) 1983-07-05 1984-06-22 Neodymlegierungen und verfahren zur herstellung derselben.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR8311139 1983-07-05
FR8311139A FR2548687B1 (fr) 1983-07-05 1983-07-05 Alliages de neodyme et leur procede de fabrication
FR838314392A FR2551769B2 (fr) 1983-07-05 1983-09-09 Alliages de neodyme et leur procede de fabrication
FR8314392 1983-09-09

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP88100014.5 Division-Into 1988-01-04

Publications (2)

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EP0134162A1 true EP0134162A1 (de) 1985-03-13
EP0134162B1 EP0134162B1 (de) 1989-08-30

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Family Applications (2)

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EP88100014A Expired - Lifetime EP0272250B1 (de) 1983-07-05 1984-06-22 Verfahren zur Herstellung von Neodymlegierungen
EP84401307A Expired EP0134162B1 (de) 1983-07-05 1984-06-22 Neodymlegierungen und Verfahren zur Herstellung derselben

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EP88100014A Expired - Lifetime EP0272250B1 (de) 1983-07-05 1984-06-22 Verfahren zur Herstellung von Neodymlegierungen

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US (1) US4636353A (de)
EP (2) EP0272250B1 (de)
JP (1) JPS6046346A (de)
KR (1) KR920006603B1 (de)
AU (1) AU579579B2 (de)
BR (1) BR8403289A (de)
CA (1) CA1253721A (de)
DE (2) DE3479595D1 (de)
FR (1) FR2551769B2 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3636643A1 (de) * 1985-10-28 1987-04-30 Us Energy Herstellung von seltenerd-eisen-legierungen durch thermit-reduktion
US4767455A (en) * 1986-11-27 1988-08-30 Comurhex Societe Pour La Conversion De L'uranium En Metal Et Hexafluorure Process for the preparation of pure alloys based on rare earths and transition metals by metallothermy
EP0254251A3 (en) * 1986-07-21 1989-01-25 Hitachi Metals, Ltd. Method of producing neodymium-iron-boron permanent magnet
RU2210607C1 (ru) * 2001-12-27 2003-08-20 Институт химии и технологии редких элементов и минерального сырья им. И.В.Тананаева Кольского научного центра РАН Способ получения сплава на основе переходного и редкоземельных элементов и устройство для его осуществления

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US5073337A (en) * 1990-07-17 1991-12-17 Iowa State University Research Foundation, Inc. Rare earth/iron fluoride and methods for making and using same
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US5129945A (en) * 1990-10-24 1992-07-14 The United States Of America As Represented By The Secretary Of The Interior Scrap treatment method for rare earth transition metal alloys
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US5238489A (en) * 1992-06-30 1993-08-24 The United States Of America As Represented By The Secretary Of The Interior Leaching/flotation scrap treatment method
US6755924B2 (en) 2001-12-20 2004-06-29 General Electric Company Method of restoration of mechanical properties of a cast nickel-based super alloy for serviced aircraft components
US8109349B2 (en) 2006-10-26 2012-02-07 Schlumberger Technology Corporation Thick pointed superhard material
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US8540037B2 (en) * 2008-04-30 2013-09-24 Schlumberger Technology Corporation Layered polycrystalline diamond
US20110126550A1 (en) * 2008-07-08 2011-06-02 Technical University Of Denmark Magnetocaloric refrigerators
WO2010117765A1 (en) * 2009-03-30 2010-10-14 Schlumberger Canada Limited Double sintered thermally stable polycrystalline diamond cutting elements
BR112014008599B1 (pt) 2011-10-20 2019-11-05 Akzo Nobel Chemicals Int Bv processo em que uma alimentação líquida compreendendo ácido monocloroacético, ácido dicloroacético e opcionalmente ácido acético e/ou ácido tricloroacético é submetida a uma etapa de hidrodescloração catalítica
PL2748138T3 (pl) 2011-10-20 2017-09-29 Akzo Nobel Chemicals International B.V. Proces oczyszczania ciekłego wsadu zawierającego mca i dca
RU2596563C1 (ru) * 2015-04-23 2016-09-10 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Способ получения магнитотвердого материала
CN114891953B (zh) * 2022-03-31 2024-03-08 包头市英思特稀磁新材料股份有限公司 一种提高烧结钕铁硼出材率的方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3636643A1 (de) * 1985-10-28 1987-04-30 Us Energy Herstellung von seltenerd-eisen-legierungen durch thermit-reduktion
EP0254251A3 (en) * 1986-07-21 1989-01-25 Hitachi Metals, Ltd. Method of producing neodymium-iron-boron permanent magnet
US4767455A (en) * 1986-11-27 1988-08-30 Comurhex Societe Pour La Conversion De L'uranium En Metal Et Hexafluorure Process for the preparation of pure alloys based on rare earths and transition metals by metallothermy
RU2210607C1 (ru) * 2001-12-27 2003-08-20 Институт химии и технологии редких элементов и минерального сырья им. И.В.Тананаева Кольского научного центра РАН Способ получения сплава на основе переходного и редкоземельных элементов и устройство для его осуществления

Also Published As

Publication number Publication date
DE3479595D1 (en) 1989-10-05
DE3485950D1 (de) 1992-11-05
EP0272250A1 (de) 1988-06-22
US4636353A (en) 1987-01-13
BR8403289A (pt) 1985-06-18
AU3008184A (en) 1985-01-10
AU579579B2 (en) 1988-12-01
EP0272250B1 (de) 1992-09-30
CA1253721A (fr) 1989-05-09
FR2551769A2 (fr) 1985-03-15
JPH0224902B2 (de) 1990-05-31
KR850001297A (ko) 1985-03-18
JPS6046346A (ja) 1985-03-13
FR2551769B2 (fr) 1990-02-02
KR920006603B1 (ko) 1992-08-10
DE3485950T2 (de) 1993-02-25
EP0134162B1 (de) 1989-08-30

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