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EP0320064A1 - Hard magnetic material of a rare earth metal, iron and carbon - Google Patents
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EP0320064A1 - Hard magnetic material of a rare earth metal, iron and carbon - Google Patents

Hard magnetic material of a rare earth metal, iron and carbon Download PDF

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Publication number
EP0320064A1
EP0320064A1 EP88202784A EP88202784A EP0320064A1 EP 0320064 A1 EP0320064 A1 EP 0320064A1 EP 88202784 A EP88202784 A EP 88202784A EP 88202784 A EP88202784 A EP 88202784A EP 0320064 A1 EP0320064 A1 EP 0320064A1
Authority
EP
European Patent Office
Prior art keywords
magnetic material
hard magnetic
carbon
iron
composition
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.)
Withdrawn
Application number
EP88202784A
Other languages
German (de)
French (fr)
Inventor
Dirk Bastiaan De Mooij
Kurt Heinz Jürgen Buschow
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.)
Koninklijke Philips NV
Original Assignee
Philips Gloeilampenfabrieken NV
Koninklijke Philips Electronics NV
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 NL8702991A external-priority patent/NL8702991A/en
Application filed by Philips Gloeilampenfabrieken NV, Koninklijke Philips Electronics NV filed Critical Philips Gloeilampenfabrieken NV
Publication of EP0320064A1 publication Critical patent/EP0320064A1/en
Withdrawn legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047Alloys characterised by their composition
    • H01F1/053Alloys characterised by their composition containing rare earth metals
    • H01F1/055Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/058Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IVa elements, e.g. Gd2Fe14C

Definitions

  • the invention relates to a hard magnetic material comprising neodymium, iron and carbon.
  • Nd2Fe14B having the tetragonal crystal structure. It is known that in this compound substitution of B by C leads to an increased anisotropy (see, for example, Journal de Physique Colloque C6, supplphi au no. 9, T 46, Sept. 1985, page C6-305/308: "Magnetic Anisotropy of Carbon Doped Nd2Fe14B" by Bolzoni, Leccabue, Pareti and Sanchez). In this article it is stated on page 306 that it was impossible to obtain the tetragonal phase when borium was completely substituted by carbon in the compound Nd2Fe14B. This is also stated in an article in Solid State Communications Vol. 64, No. 5 p. 639-644 (1987).
  • this object could be achieved by means of a material which has the tetragonal crystal structure and which consists of a recrystallization annealed cast material having a composition which does not or hardly deviate from the stoichiometric composition Nd2Fe14C.
  • Fe may be substituted by Co up to a maximum of 6 at.% calculated on the overall composition. If more than 6 at.% of Fe is substituted by Co the quantity of hard magnetic material having the tetragonal crystal structure, which can be obtained in the annealing treatment decreases significantly.
  • the hard magnetic material in accordance with the invention can be obtained as follows.
  • the starting materials neodymium, iron, (possibly) cobalt and carbon are melted together in a substantially stoichiometric ratio, preferably, under an inert gas atmosphere such as argon.
  • the melt is cast in a mould.
  • the material has the Nd2Fe17 structure and is not hard magnetic; the carbon is dissolved in the lattice. It is assumed that the carbon in the lattice could substitute one or more iron atoms.
  • the structure is rhombohedral. If desired, the casting obtained can be homogenization annealed at a temperature of 900° or higher.
  • the material only comprises neodymium, iron and carbon it is annealed at a temperature between 840 and 890° C so that recrystallization takes place. It has been found that recrystallization takes place only within this temperature range, thereby forming the tetragonal Nd2Fe14C phase. Surprisingly it has been found that on weighing out the starting materials it is undesirable to clearly deviate from the stoichiometric composition as is required in the case of the corresponding boron compounds. A small positive deviation of no more than 20% in the quantity of neodymium and/or carbon relative to the stoichiometric composition and of 15% in the quantity of iron, however, has been found permissible.
  • the tetragonal phase is not formed outside the indicated temperature range (above 890° C) or, if said phase is formed, predominantly, a second phase having the Nd2Fe17 structure remains in addition to the tetragonal phase (below 840° C). If annealing is carried out in the indicated temperature range the tetragonal phase is predominantly formed.
  • a substantially single-phase material having optimum magnetic properties can be obtained if annealing is carried out at temperatures between 850 and 880° C, preferably at 870° C. If the material also comprises Co, the annealing process in which recrystallization takes place is preferably carried out at a temperature of approximately 850° C.
  • Magnets can be obtained by directly casting the material in the desired shape. After casting and recrystallization annealing the material can be powdered and subsequently sintered to the desired shape in a magnetic field or be mixed with synthetic resin and pressed into the desired shape.
  • part of the iron may be substituted by other 3d metals and/or aluminium, gallium, silicon etc.
  • Part of the neodymium can be substituted by one or more rare earth metals.
  • a casting was manufactured, the overall composition of which corresponded to the formula Nd2Fe13CoC. Subsequently, this casting was directly subjected to a recrystallization annealing process at 850° C for 150 hours without being previously homogeneization annealed.
  • the material thus obtained is substantially single phase and has a tetragonal crystal structure.
  • the material has a Curie temperature of 620 K.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

A hard magnetic material having the substantially stoichiometric composition Nd2Fe14C. It can be obtained by casting and subsequently recrystallization annealing at a temperature between 840 and 890 DEG C. A part of Fe may be substituted by Co. In this case the magnetic material is obtained by casting and subsequently recrystallization annealing at a temperature of approximately 850 DEG C.

Description

  • The invention relates to a hard magnetic material comprising neodymium, iron and carbon.
  • A known material of this type is Nd₂Fe₁₄B having the tetragonal crystal structure. It is known that in this compound substitution of B by C leads to an increased anisotropy (see, for example, Journal de Physique Colloque C6, supplément au no. 9, T 46, Sept. 1985, page C6-305/308: "Magnetic Anisotropy of Carbon Doped Nd₂Fe₁₄B" by Bolzoni, Leccabue, Pareti and Sanchez). In this article it is stated on page 306 that it was impossible to obtain the tetragonal phase when borium was completely substituted by carbon in the compound Nd₂Fe₁₄B. This is also stated in an article in Solid State Communications Vol. 64, No. 5 p. 639-644 (1987). In this article "Synthesis and Magnetic Properties of Ternary Carbides R₂Fe₁₄C" by Gueramiom, Bezinge, Yvon and Muller it is stated on page 640 that the tetragonal structure in, amongst others, R = neodymium is not found by means of recrystallization annealing.
  • It is an object of the invention to provide a hard magnetic material having a high crystal anisotropy, which comprises only carbon instead of boron and also a relatively high content of neodymium.
  • It was found that this object could be achieved by means of a material which has the tetragonal crystal structure and which consists of a recrystallization annealed cast material having a composition which does not or hardly deviate from the stoichiometric composition Nd₂Fe₁₄C. In this composition Fe may be substituted by Co up to a maximum of 6 at.% calculated on the overall composition. If more than 6 at.% of Fe is substituted by Co the quantity of hard magnetic material having the tetragonal crystal structure, which can be obtained in the annealing treatment decreases significantly.
  • The hard magnetic material in accordance with the invention can be obtained as follows. The starting materials neodymium, iron, (possibly) cobalt and carbon are melted together in a substantially stoichiometric ratio, preferably, under an inert gas atmosphere such as argon. The melt is cast in a mould. The material has the Nd₂Fe₁₇ structure and is not hard magnetic; the carbon is dissolved in the lattice. It is assumed that the carbon in the lattice could substitute one or more iron atoms. The structure is rhombohedral. If desired, the casting obtained can be homogenization annealed at a temperature of 900° or higher. If the material only comprises neodymium, iron and carbon it is annealed at a temperature between 840 and 890° C so that recrystallization takes place. It has been found that recrystallization takes place only within this temperature range, thereby forming the tetragonal Nd₂Fe₁₄C phase. Surprisingly it has been found that on weighing out the starting materials it is undesirable to clearly deviate from the stoichiometric composition as is required in the case of the corresponding boron compounds. A small positive deviation of no more than 20% in the quantity of neodymium and/or carbon relative to the stoichiometric composition and of 15% in the quantity of iron, however, has been found permissible. The tetragonal phase is not formed outside the indicated temperature range (above 890° C) or, if said phase is formed, predominantly, a second phase having the Nd₂Fe₁₇ structure remains in addition to the tetragonal phase (below 840° C). If annealing is carried out in the indicated temperature range the tetragonal phase is predominantly formed. A substantially single-phase material having optimum magnetic properties can be obtained if annealing is carried out at temperatures between 850 and 880° C, preferably at 870° C. If the material also comprises Co, the annealing process in which recrystallization takes place is preferably carried out at a temperature of approximately 850° C. It has been found that cobalt considerably increases the Curie temperature of the hard magnetic material, which may be desirable for certain applications. In the manufacture of the Co-containing hard magnetic materials in accordance with the invention, it has been found that on weighing out the individual elements a small deviation from the stoichiometric composition is not necessary, but it is permissible. A positive deviation of 20% in the quantity of neodymium and/or carbon as well as a positive deviation of 15% in the quantity of iron and/or cobalt is permissible. The experiments leading to the invention were also carried out using praseodymium instead of neodymium; it was found impossible to obtain a substantially single-phase material having the tetragonal crystal structure.
  • Example 1:
  • As has been described above, castings were manufactured having the overall composition Nd₂Fe₁₄C. After casting the material had a Nd₂Fe₁₇ structure (rhombohedral). Without previous homogenization annealing the castings obtained were directly recrystallization annealed for 500 hours at 870° C. The material was single phase and had a tetragonal crystal structure. The lattice constants were measured. It was found that: A = 8.814 Å, C = 12.015 Å. The material in accordance with the invention has a Curie temperature of 535 K. The saturation magnetization at 20° C= 130 EMU per gram. Single-phase materials having the tetragonal crystal structure were obtained in the same manner using materials having the overall composition Nd12.1Fe81.8C₆ and Nd11.8Fe81.1C7.1.
  • Magnets can be obtained by directly casting the material in the desired shape. After casting and recrystallization annealing the material can be powdered and subsequently sintered to the desired shape in a magnetic field or be mixed with synthetic resin and pressed into the desired shape.
    In the said materials, part of the iron may be substituted by other 3d metals and/or aluminium, gallium, silicon etc. Part of the neodymium can be substituted by one or more rare earth metals.
  • Example 2:
  • A casting was manufactured, the overall composition of which corresponded to the formula Nd₂Fe₁₃CoC. Subsequently, this casting was directly subjected to a recrystallization annealing process at 850° C for 150 hours without being previously homogeneization annealed. The material thus obtained is substantially single phase and has a tetragonal crystal structure. The material has a Curie temperature of 620 K.

Claims (9)

1. A hard magnetic material comprising a rare earth metal, iron and carbon, characterized in that the material consists of a recrystallization annealed cast material having a tetragonal crystal structure and a composition which does not or hardly deviate from the stoichiometric composition Nd₂Fe₁₄C.
2. A hard magnetic material as claimed in Claim 1, characterized in that a maximum of 6 at.% of the Fe present in the hard magnetic material, calculated on the overall composition, has been substituted by Co.
3. A hard magnetic material as claimed in Claim 1, characterized in that as regards neodymium and carbon the composition's positive deviation from the stoichiometric composition does not exceed 20%, and as regards iron the positive deviation does not exceed 15%.
4. A hard magnetic material as claimed in Claim 3, characterized in that as regards Nd and C the composition's positive deviation from the stoichiometric composition does not exceed 20%, and as regards iron and cobalt the positive deviation does not exceed 15%.
5. A hard magnetic material as claimed in Claim 3, characterized in that the lattice constants amount to A = 8.814 Å and C = 12.015 Å.
6. A method of manufacturing a hard magnetic material comprising neodymium, iron and carbon, characterized in that the starting materials neodymium, ion and carbon are melted together in a quantity which deviates little from the stoichiometric ratio Nd₂Fe₁₄C, and cast in a mould, after which the casting is recrystallization annealed at a temperature between 840 and 890° C.
7. A method as claimed in Claim 6, characterized in that the material is annealed at a temperature between 850 and 880° C.
8. A method of manufacturing a hard magnetic material comprising neodymium, iron, cobalt and carbon, characterized in that the starting materials neodymium, iron, cobalt and carbon are melted together in a quantity which deviates little from the stoichiometric ratio Nd₂Fe14-xCoxC (wherein x < 1.02) and cast in a mould, after which the casting is recrystallization annealed at a temperature of approximately 850° C.
9. Magnetic castings comprising a hard magnetic material as claimed in anyone of the Claims 1 upto and including 5, and/or magnetic castings obtained by means of a method as claimed in anyone of the Claims 6 up to and including 8.
EP88202784A 1987-12-11 1988-12-05 Hard magnetic material of a rare earth metal, iron and carbon Withdrawn EP0320064A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
NL8702991 1987-12-11
NL8702991A NL8702991A (en) 1987-12-11 1987-12-11 Boron-free hard magnetic material comprising a tetragonal phase - by annealing castings of an alloy contg. neodymium, iron and carbon and having a specific stoichiometric compsns.
NL8800740A NL8800740A (en) 1987-12-11 1988-03-24 HARD-MAGNETIC MATERIAL FROM A RARE NATURAL METAL, IRON AND CARBON.
NL8800740 1988-03-24

Publications (1)

Publication Number Publication Date
EP0320064A1 true EP0320064A1 (en) 1989-06-14

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EP88202784A Withdrawn EP0320064A1 (en) 1987-12-11 1988-12-05 Hard magnetic material of a rare earth metal, iron and carbon

Country Status (5)

Country Link
EP (1) EP0320064A1 (en)
JP (1) JPH024940A (en)
KR (1) KR890010944A (en)
CN (1) CN1033494A (en)
NL (1) NL8800740A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3928389A1 (en) * 1989-08-28 1991-03-14 Schramberg Magnetfab PERMANENT MAGNET
US5062907A (en) * 1989-05-10 1991-11-05 U.S. Philips Corp. Hard magnetic material and magnet manufactured from such hard magnetic material
EP0468449A1 (en) * 1990-07-24 1992-01-29 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Bonded rare earth magnet and a process for manufacturing the same
US5240627A (en) * 1990-07-24 1993-08-31 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Bonded rare earth magnet and a process for manufacturing the same
US5300156A (en) * 1990-07-24 1994-04-05 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Bonded rare earth magnet and a process for manufacturing the same
DE4242839A1 (en) * 1992-12-17 1994-06-23 Siemens Ag Mfr. of magnetic anisotropic power of rare earth based compound
DE4243048A1 (en) * 1992-12-18 1994-06-23 Siemens Ag Manufacturing hard magnetic materials using Sm Fe C system
US5478411A (en) * 1990-12-21 1995-12-26 Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin Magnetic materials and processes for their production
CN120933012A (en) * 2025-07-23 2025-11-11 北京工业大学 Rare earth iron carbon-based thermal deformation magnet and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105603296A (en) * 2015-12-23 2016-05-25 桂林电子科技大学 Rare earth Fe-based electromagnetic shielding material and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF APPLIED PHYSICS, PROCEEDINGS OF THE THIRTY-FIRST ANNUAL CONFERENCE ON MAGNETISM AND MAGNETIC MATERIALS, vol. 61, no. 8, part 11A, 15th Aptil 1987, pages 3574-3577, American Institute of Physics, New York, US; N.C. LIU et al.: "High intrinsic coercivities in iron-rare earth-carbon-boron alloys through the carbide or boro-carbide Fe14R2X(X=BxC1-x) *
MATERIALS LETTERS, vol. 4, nos. 8-9, August 1986, pages 377-380, Elsevier Science Publishers, N.V., Amsterdam, NL; N.C. LIU et al.: "High coercivity permanent magnet materials based on iron-rare-earth-carbon alloys" *
PATENT ABSTRACTS OF JAPAN, vol. 4, no. 109 (E-20)[591], 6th August 1980, page 92 E 20; & JP-A-55 67 110 (SUWA SEIKOSHA K.K.) 21-05-1980 *
SOLID STATE COMMUNICATIONS, vol. 64, no. 5, 1987, pages 639-644, Pergamon Journals Ltd, London, GB; M. GUERAMIAN et al.: "Synthesis and magnetic properties of ternary carbides R2Fe14C(R = Pr,Sm,Gd,Tb,Dy,Ho,Er,Tm,Lu) with Nd2Fe14B structure type" *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5062907A (en) * 1989-05-10 1991-11-05 U.S. Philips Corp. Hard magnetic material and magnet manufactured from such hard magnetic material
DE3928389A1 (en) * 1989-08-28 1991-03-14 Schramberg Magnetfab PERMANENT MAGNET
EP0468449A1 (en) * 1990-07-24 1992-01-29 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Bonded rare earth magnet and a process for manufacturing the same
US5240627A (en) * 1990-07-24 1993-08-31 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Bonded rare earth magnet and a process for manufacturing the same
US5300156A (en) * 1990-07-24 1994-04-05 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Bonded rare earth magnet and a process for manufacturing the same
US5478411A (en) * 1990-12-21 1995-12-26 Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin Magnetic materials and processes for their production
DE4242839A1 (en) * 1992-12-17 1994-06-23 Siemens Ag Mfr. of magnetic anisotropic power of rare earth based compound
DE4243048A1 (en) * 1992-12-18 1994-06-23 Siemens Ag Manufacturing hard magnetic materials using Sm Fe C system
CN120933012A (en) * 2025-07-23 2025-11-11 北京工业大学 Rare earth iron carbon-based thermal deformation magnet and preparation method thereof

Also Published As

Publication number Publication date
JPH024940A (en) 1990-01-09
KR890010944A (en) 1989-08-11
NL8800740A (en) 1989-07-03
CN1033494A (en) 1989-06-21

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