CN1033495A - No boron hard magnetic material with magnetic four directions crystalline phase - Google Patents

No boron hard magnetic material with magnetic four directions crystalline phase Download PDF

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Publication number
CN1033495A
CN1033495A CN88108566A CN88108566A CN1033495A CN 1033495 A CN1033495 A CN 1033495A CN 88108566 A CN88108566 A CN 88108566A CN 88108566 A CN88108566 A CN 88108566A CN 1033495 A CN1033495 A CN 1033495A
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CN
China
Prior art keywords
hard magnetic
composition
magnetic material
following
boron
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CN88108566A
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Chinese (zh)
Inventor
赖恩德·科胡恩
约翰·菲利普·威廉·杜萨托
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Koninklijke Philips NV
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Philips Gloeilampenfabrieken NV
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Publication of CN1033495A publication Critical patent/CN1033495A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets 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
    • H01F1/04—Magnets 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
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/058—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IVa elements, e.g. Gd2Fe14C

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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)
  • Carbon And Carbon Compounds (AREA)

Abstract

A kind of based on neodymium, iron and carbon, particle diameter is equal to or less than 0.2 μ m and the thin brilliant cubic no boron hard magnetic material mutually of Hard Magnetic arranged, this material has Nd 2Fe 14C-structure.Can be by the spray coating alloy of fusion being formed thickness 30 μ m in the quenching of rapid movement surface or thinner tablet obtains this material, Zhi Bei material is annealed in from 685 to 730 ℃ temperature range more like this, just forms needed structure.

Description

No boron hard magnetic material with magnetic four directions crystalline phase
The present invention relates to based on neodymium, the no boron hard magnetic material of iron and carbon, it has Hard Magnetic four directions crystalline phase.The invention still further relates to this preparation methods.
This class known materials comprises Nd 2Fe 14B, it has as Hard Magnetic crystalline phase tetragonal crystal structure.Known in this compound part of boron is replaced with carbon, then caused strengthening anisotropic properties (for example, the Journal de Physique Colloque C6 of magnetic, supplement au no.9, T.46, Sept 1985, page C6-305/308: " mix the Nd of carbon 2Fe 14The magnetic anisotropy of B " by Bolzoni, Leccabue, Pareti and Sanchez).Point out the 306th page of this piece paper: when boron is replaced by carbon fully, then can not obtain cubic crystalline phase, and the latter is desired for obtaining desirable Hard Magnetic characteristic.
The purpose of this invention is to provide and have strong anisotropic hard magnetic material; This material comprises iron, neodymium, and the carbon of unique replacement boron.
Have been found that the material of forming with following composition, that is,
Nd 11.2 to 15.2at%
Fe 74.8 to 84.8at%
C 4 to 10at%
Can reach this purpose; This material has the cubic crystalline phase of fine crystallization, and its particle diameter is 0.2 μ m or littler, and, have Nd 2Fe 14C-structure.The mentioned component scope comprises the material composition with 0.6T or bigger coercive force μ oHc.Should be pointed out that if select following material composition for use:
Nd：12-15at·%
Fe：75-84at·%
C 4.8-10at·%
Can obtain the maximum magnetic flux coercive force.But, if select following material composition for use:
Nd： 12.0-14.2at·%
Fe： 76.6-83.2at·%
C： 4.8-9.2at·%
Then the magnetic of material can improve, and the Curie temperature of these materials is generally 260 ℃ or higher.Even so, this material also comprises the second soft magnetism crystalline phase sometimes.Single-phase material generally has following composition substantially:
Nd：12-14at·%
Fe：78-81at·%
C：6-8at·%
The composition of material of the present invention has known Nd 2Fe 14The character of B material in these materials, is replaced iron rule with cobalt and has been improved Curie temperature.
Self-evident, the fine crystallization body of indication of the present invention is meant that at least 90% Hard Magnetic phase crystalline solid has 0.2 μ m or littler size.The method that obtains hard magnetic material of the present invention is:, then, melt is sprayed on the quenching surface with respect to the spray orifice high-speed motion with raw materials melt together, for example, on the atwirl copper panel surface of spray orifice.
European patent application EP-A108474 provides the preparation method of banded hard magnetic material.In this known method, the quenching surface of motion is that the circumferential surface by highly heat-conductive material (as the copper of chromium plating) disk is constituted.
As long as make suitable modification, this method can be used for preparing the thin brilliant hard magnetic material of no boron based on neodymium and iron equally, but this european patent application had not been pointed out this point.In research of the present invention, have been found that.Quick cooling carbon containing does not have the boron neodymium-iron alloy and does not form desirable tetragonal structure crystalline phase.If by suitably selecting spray pressure, the crack size, the interval of crack and disc rotation speed on the disk, can obtain thickness in spraying process is 30 μ m or more thinner sheet or ribbon, so, desirable result can enough obtain in the cooling procedure fast a kind of.Formed or ribbon have the crystallite phase, and its structure resembles Nd very much 2Fe 17; But this plants and herds happiness emperor timid pool and twist 1 box spoon and show favour to together with fine jade and closely question the capsule chaff hemorrhoid of wandering and both offered the edge bright  that dies young to and criticize sb's faults frankly the  legendary bird with poisonous feathers and herd rare T posthumous title ticket Liao d in Job's tears supper squid little T much strong Gui  bitter edible plant convulsion ⒚ demons and monsters  ticket Fu Mu Mu tall building of standing up of ticking of standing up 2Fe 17Under the temperature of phase, boron does not dissolve basically.
According to a further aspect in the invention,, this material is handled through very of short duration lower temperature recrystallization annealing, then can be obtained desirable hard magnetic material if after the melt spraying.
Find that unexpectedly in this annealing in process, generation has tetragonal and Nd basically 2Fe 14The crystallite phase of C composition, some unnecessary carbon can also be dissolved in this mutually in.
This annealing in process is to carry out under the temperature between 675 to 750 ℃, as carry out between 685 ℃ to 730 ℃ of the temperature then better.When being heated to 720 ℃, the cubic phase Nd of desirable thin crystalline substance 2Fe 14C forms after reaching described temperature one minute.The required annealing time of crystallization process can be easy to find out under any annealing temperature in the temperature range of appointment by experiment.Suitable annealing in process is: material was kept in 720 ℃ furnace temperature 1 to 5 minute.In fact, the dwell was suitable at 2 to 3 minutes.The material of Huo Deing has suitable permanent-magnetic property like this.Record saturation magnetization μ oHsat＞1.2T, magnetic remanence μ oHr＞0.50T and coercive force μ oHc＞1.0T.The specific example of new magnetic material is: at 680 ℃ of very high coercive forces through 6 days back μ oHc=0.75T of also having that anneal.When tangible grain growth after 800 ℃ long-time (360 hours) heating, in material of the present invention, occurring, at this moment, form crystal grain with size between 0.2 to the 0.6 μ m.In this process, coercive force drops to 0.2T.When observing crystal grain and further increase after 15 days in heating under 850 ℃ to 900 ℃.At this moment, topmost crystalline phase or Nd 2Fe 14The C crystalline phase.
Of the present invention studies confirm that: after the composition of neodymium in the material is less than the processing of 720 ℃ of 11.2at%, annealed temperature, form crystalline phase more than α-Fe structure of 10%; A certain amount of carbon can be dissolved in this crystalline phase, at this moment, does not observe the vestige of neodymium with the X-ray radiography method.If the content of neodymium is more than 15.2at% in the material, then do not form cubic crystalline phase Nd 2Fe 14C perhaps have only micro-this crystalline phase, and this material is in dominant Nd with rhombohedral structure 2Fe 17In the crystalline phase, carbon dissolution is in this crystalline phase.Certainly, other technology of cooling off molten alloy fast also can be used, and also can obtain same result.
When making magnet, flaky material (for example 650 ℃) under heating condition is squeezed into magnet, if desired, also can be with tablet granulating or grinding.Tablet can be used synthetic resin adhesive, if desired, with its granulating or grinding, makes magnet.
The advantage of new magnetic material is not form poisonous boron-containing compound in preparation process when contacting with water and/or argon.
Embodiment 1
With composition is neodymium 13.5at%, and the 20 gram alloys of iron 79.6at% and carbon 6.9at% are heated to 1300 ℃, make it to melt.Liquid alloy is sprayed onto on the copper dish by the hole of 0.4mm * 10mm.Distance from the fenestra to the plate is 0.2mm, and spray pressure is 2 * 10 4Pa, and plate is 28m/S with respect to the movement velocity of fenestra.Flow rate is 5cm 3/ S sprays in argon gas.So just obtain wide about 10mm, average length is 10mm and thickness is the ribbon of 20 μ m.Then, the tablet that obtains put into be heated to 720 ℃ in the stove, and, being incubated 3 minutes, the material that so obtains is with thin brilliant tetragonal body structure (Nd 2Fe 14C) composition is main.Crystallite dimension (more than 90%): 0.2 μ m.
Measure following magnetic:
Coercive force μ oHc: 1.02T
Saturation magnetization μ oHsat: 1.34T
Magnetic remanence μ oHr: 0.72T
Curie temperature: 269 ℃
Embodiment 2
The material of the listed composition of following table is handled by same mode fully, wherein lists the character that measures from this crystalline material:
Material composition coercive force saturation magnetization magnetic remanence
μoHc（T） μoHsat（T） μoHr（T）
Nd 13.3Fe 80.9C 5.80.65 1.31 0.55
Nd 13.5Fe 77.7C 8.80.60 1.33 0.64
Nd 14.8Fe 76.4C 8.81.16 1.32 0.70

Claims (15)

1, a kind of based on neodymium, the no boron hard magnetic material of iron and carbon, this material have Hard Magnetic four directions phase, it is characterized in that containing following total composition:
Nd 11.2-15.2at·%
Fe 74.8-84.8at·%
C 4-10at·%
This material is the cubic phase of thin crystalline substance, and its particle diameter is 0.2 μ m or littler, and Nd is arranged 2Fe 14C-structure.
2,, it is characterized in that this material is made up of following composition as the desired no boron hard magnetic material of claim 1:
Nd 12-15at·%
Fe 75-84at·%
C 4.8-10at·%
3,, it is characterized in that this material is made up of following composition as the desired no boron hard magnetic material of claim 2:
Nd 12.0-14.2at·%
Fe 76.6-83.2at·%
C 4.8-9.2at·%
4,, it is characterized in that this material is made up of following composition as the desired no boron hard magnetic material of claim 3:
Nd 12-14at·%
Fe 78-81at·%
C 6-8at·%
5,, it is characterized in that this material is made up of following composition as the desired no boron hard magnetic material of claim 4:
Nd 13.5at·%
Fe 79.6at·%
C 6.9at·%
6, as each desired no boron hard magnetic material in the above claim, it is characterized in that: in total composition, a part of iron is enough to improve the cobalt of the some of Curie temperature and is replaced.
7, a kind of based on neodymium, the preparation method of the hard magnetic material of iron and carbon be the spray coating alloy of fusing in the quenching surface of rapid movement, further handle band or the sheet that obtains so again, it is characterized in that this method has following steps:
By alloy with following total composition:
Nd 11.2-15.2at·%
Fe 74.8-84.8at·%
C 4-10at·%
Making thickness is 30 μ m or thinner band or sheet, the material of such acquisition is annealed in temperature range is 675 to 750 ℃ environment again.
8, as the desired method of claim 7, the annealing region that it is characterized in that this material is 685-730 ℃.
9, as the desired method of claim 8, the annealing temperature that it is characterized in that this material is 720 ℃.
10, as the desired method of claim 7, it is characterized in that using alloy with following total composition:
Nd 12-15.2at·%
Fe 76.6-83.2at·%
C 4.8-9.2at·%
11, as the desired method of claim 7, it is characterized in that using alloy with following total composition:
Nd 12.0-14.2at·%
Fe 76.6-83.2at·%
C 4.8-9.2at·%
12, as the desired method of claim 11, it is characterized in that using alloy with following total composition:
Nd 12-14at·%
Fe 78-81at·%
C 6-8at·%
13, as the desired method of claim 12, it is characterized in that using alloy with following total composition:
Nd 13.5at·%
Fe 79.6at·%
C 6.9at·%
14, with the magnet of making as material composition in the claim 1 to 6.
15, with the magnet of as claim 7 to 13, making that material obtained.
CN88108566A 1987-12-11 1988-12-08 No boron hard magnetic material with magnetic four directions crystalline phase Pending CN1033495A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8702992A NL8702992A (en) 1987-12-11 1987-12-11 BORIUM-FREE HARD-MAGNETIC MATERIAL, CONTAINING A MAGNETIC TETRAGONAL PHASE.
NL8702992 1987-12-11

Publications (1)

Publication Number Publication Date
CN1033495A true CN1033495A (en) 1989-06-21

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CN88108566A Pending CN1033495A (en) 1987-12-11 1988-12-08 No boron hard magnetic material with magnetic four directions crystalline phase

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EP (1) EP0320063A1 (en)
JP (1) JPH01192714A (en)
KR (1) KR890010945A (en)
CN (1) CN1033495A (en)
NL (1) NL8702992A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101684527B (en) * 2008-09-22 2011-01-12 中国科学院宁波材料技术与工程研究所 Method for preparing manganese-aluminium hard-magnetic alloy

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2034632C (en) * 1990-02-20 1997-05-13 Carlton Dwight Fuerst Hot worked rare earth-iron-carbon magnets

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101684527B (en) * 2008-09-22 2011-01-12 中国科学院宁波材料技术与工程研究所 Method for preparing manganese-aluminium hard-magnetic alloy

Also Published As

Publication number Publication date
JPH01192714A (en) 1989-08-02
KR890010945A (en) 1989-08-11
EP0320063A1 (en) 1989-06-14
NL8702992A (en) 1989-07-03

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