EP0505348B1 - Permanent magnet material or sintered magnet and fabrication process - Google Patents
Permanent magnet material or sintered magnet and fabrication process Download PDFInfo
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- EP0505348B1 EP0505348B1 EP92890055A EP92890055A EP0505348B1 EP 0505348 B1 EP0505348 B1 EP 0505348B1 EP 92890055 A EP92890055 A EP 92890055A EP 92890055 A EP92890055 A EP 92890055A EP 0505348 B1 EP0505348 B1 EP 0505348B1
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- hard magnetic
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- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 230000005291 magnetic effect Effects 0.000 claims abstract description 78
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
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- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 description 8
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- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- 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
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
Definitions
- the invention relates to a sintered permanent magnet (material) containing 8 to 30 at.% Rare earths (SE), 2 to 28 at.% Boron (B), remainder iron (Fe) or iron and cobalt (Co) a hard magnetic component or with a hard magnetic phase of the Se 2 Fe 14 B type, it being possible for some of the Fe atoms to be replaced by Co atoms.
- SE Rare earths
- B Boron
- Fe remainder iron
- Co cobalt
- Permanent magnets or permanent materials made essentially of an alloy of iron (Fe), optionally cobalt (Co), boron (B) and rare earth (SE) sintered, are preferably used when high coercive force, high remanence and / or large Energy product are required.
- the component forming or containing the magnetic phase of the Se 2 Fe 14 B type, some of the Fe atoms being able to be replaced by Co atoms, is produced and pulverized by melt metallurgy, which powder, optionally mixed with additives, is pressed into a green compact in a magnetic field and this is sintered and the sintered body can optionally be subjected to at least one further heat treatment.
- An SE-Fe-B permanent magnet material in which an alloy additive containing an element from the group of the heavy SE and / or SSE compounds, optionally with grain boundary additives, is added to the grain boundaries of the grains, which are formed from a magnetic phase is disclosed by EP-A-0395625.
- a sintered magnet is known from WO-A-8902156, the structure of which is free of large Fe 4 NdB 4 grains and the composition of which is selected such that the material at sintering temperature is in a two-phase area, namely in a hard magnetic phase and an Nd-rich phase.
- EP-A-0425469 relates to a sintered SE-Fe-B permanent magnet (material) in which the local concentration of the SE content increases essentially at the grain boundaries of the magnetic phase, that is to say that an inhomogeneous distribution of the SE content is given.
- JP-62274046 a permanent magnet which consists of a sintered powder mixture which is formed from at least two types of powder.
- Nd 2 Fe 14 B 6 i.e. a hard magnetic phase
- Nd paramagnetic alloy of Nd 95 Fe 5 and / or Nd 15 F 77 B 8 and / or Nd 2 FeB 16 and / or Nd 2 Fe 7 B 6 mixed.
- the invention has for its object to eliminate the disadvantages of the known SE, (FeCo), B - containing magnets (materials) and their manufacturing processes and to specify and create sintered permanent magnets, the high saturation magnetization, high coercive force and high energy product with good temperature stability and have a high Curie point at low manufacturing costs.
- Another object of the invention is to make the height of the Curie point of the permanent magnets (materials) easily adjustable according to the requirements.
- the hard magnetic component is formed from a plurality of magnetic phases which, as has been shown completely surprisingly, interact advantageously with one another. It is important here that one or more magnetic phases as the central phase or core phase are formed from surface-smoothed or diffusion-molded grains, whereby according to the latest findings, surface recrystallization can take place by diffusion and a further magnetic phase component is oriented towards the central phase as a peripheral phase or is attached to it assigns. As a result, a high proportion of magnetic volume in the material can be achieved and domain wall formation and / or domain wall displacement can be reduced, as a result of which an increase in the coercive force and consequently in the energy product occurs.
- the paramagnetic intermediate or binding phase should have a higher concentration of SE than the magnetic phases and, if appropriate, inclusions and / or additives, as a result of which a further blocking of domain walls is accomplished.
- Special magnetic properties of the material are achieved if the grains of the central or core phase have a diameter of 10 to 100 ⁇ m and the magnetic peripheral phase or phases are or are attached to the grains in a shell-like manner.
- the RE portion in the magnetic phases is essentially formed by light rare earths (LSE), in particular Nd, and the RE portion in the intermediate or binding phase contains heavy rare earths (SSE), particularly high levels become Magnetic characteristics of the magnet reached.
- LSE light rare earths
- SSE heavy rare earths
- the invention further relates to a method for producing rare earth (SE) containing (s), magnetically aligned (s), sintered (s) permanent magnet (s) according to claim 1, its base material or starting material by melt metallurgy is produced, this or this is essentially ground into powder, mixed with additives, pressed into a green body and the green body is sintered and annealed. According to the invention, such a method is characterized by the characterizing features of claim 8.
- the advantages of the invention consist in particular in that at least two magnetic phase-forming base materials or starting materials with different chemical compositions and therefore different magnetic properties are produced, comminuted into powders and mixed, as a result of which an interaction of the base materials which has a favorable influence on the magnetic characteristics can be achieved.
- a basic material is comminuted to powder with smaller particle sizes or to fine powder, which shows an earlier softening or plasticity during the sintering of the green compact pressed under magnetic field alignment and produces particularly good contact with the particles or grains of the coarse powder. This is important for the effect of the diffusion treatment or annealing, the phase boundaries being designed to be correspondingly favorable.
- the SE concentration of the base materials is dimensioned higher than that of the magnetic phase of type SE 2 (FeCo) 14 B, the compositions SE 16 (FeCo) 77 B 7 , SE 15 (Feco) having been found. 77 B 8 and SE 14 (FeCo) 80 B 6 are particularly suitable. If at least one base material is alloyed with Co and the iron portion of the magnetic phase is substituted by up to 40% with Co, particularly good temperature stability and high Curie temperatures of the magnets can be achieved.
- the SE portion of the base materials is essentially formed by LSE, the remanence and the energy product are increased.
- one or more base materials are comminuted into coarse powder with a grain diameter of 10 to 100 ⁇ m, preferably 10 to 60 ⁇ m, in particular 15 to 30 ⁇ m, and at least one further base material is ground to fine powder with a particle diameter of 0.5 to 8 ⁇ m, in particular from 3 to 8 ⁇ m, different co-contents in the coarse and fine powder further improving the magnetic characteristics.
- compounds of SSE such as, for example, Dy 2 O 3 and / or borides, for example Fe 2 B, and / or metals, for example Al, and / or oxides, for example A 12 O 3 and / or SE oxides are introduced, in particular the powders are mechanically alloyed with these substances, domain wall formation and domain wall displacement are further reduced and higher coercive forces are achieved.
- a particularly important feature of the invention is a diffusion treatment of the sintered magnet (s) (material), which is advantageously carried out at a temperature below the sintering temperature and expediently in the pendulum annealing process, because the grain surfaces of the coarse powder are smoothed and a microstructure-oriented on the smoothed grain surfaces essentially shell-like accumulation of the phase formed by the fine powder is brought about, which brings about a significant improvement in the magnetic characteristics.
- s sintered magnet
- FIG. 1 and 2 show schematically the sequence of manufacture of permanent magnet materials according to the invention.
- Table 1 shows compositions of the base materials with stoichiometric parameters.
- Table 2 shows the compositions and the magnetic characteristics of reference magnets (materials) with the designation V1 to V7.
- Tables 3a and 3b under numbers 1 to 23 list permanent magnets (materials) according to the invention.
- high magnetic characteristics at an elevated Curie temperature are achieved by the construction with a plurality of differently composed magnetic phases with diffusion molded grains and deposits.
- Table 1 Base material Range Nd 16 (Fe 1-x Co x ) 77 B 7 A Nd 15 (Fe 1-x Co x ) 77 B 8 B Nd 14 (Fe 1-x Co x ) 80 B 6 C. (Nd 1-y Dy y ) 16 Fe 77 B 7 D (Nd 1-y Dy y ) (Fe 1-x Co x ) 78 B 6 E No. Basic magnetic phase Magnetic values Ref. Troubles Vert.
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Hard Magnetic Materials (AREA)
- Powder Metallurgy (AREA)
- Manufacturing Cores, Coils, And Magnets (AREA)
- Soft Magnetic Materials (AREA)
- Magnetic Ceramics (AREA)
Abstract
Description
Die Erfindung betrifft einen gesinterten Permanentmagnet((-werkstoff) enthaltend 8 bis 30 At.-% Seltene Erden (SE), 2 bis 28 At.-% Bor (B), Rest Eisen (Fe) oder Eisen und Kobalt (Co) mit einem hartmagnetischen Anteil bzw. mit einer hartmagnetischen Phase vom Typ Se2Fe14B, wobei ein Teil der Fe-Atome durch Co-Atome ersetzt sein können.The invention relates to a sintered permanent magnet (material) containing 8 to 30 at.% Rare earths (SE), 2 to 28 at.% Boron (B), remainder iron (Fe) or iron and cobalt (Co) a hard magnetic component or with a hard magnetic phase of the Se 2 Fe 14 B type, it being possible for some of the Fe atoms to be replaced by Co atoms.
Permanentmagnete bzw. Permanentwerkstoffe aus im wesentlichen einer Legierung von Eisen (Fe), gegebenenfalls Kobalt (Co), Bor (B) und Seltenen Erden ( SE) im Sinterverfahren gefertigt, werden bevorzugt dann verwendet, wenn hohe Koerzitivkraft, hohe Remanenz und/oder großes Energieprodukt gefordert sind. Dabei wird der die magnetische Phase vom Typ Se2Fe14B, wobei ein Teil der Fe-Atome durch Co-Atome ersetzt sein können, bildende oder enthaltende Bestandteil schmelzmetallurgisch hergestellt und pulverisiert, welches Pulver gegebenenfalls mit Zusätzen vermengt im Magneffeld zu einem Grünling verpreßt und dieser gesintert wird und der Sinterkörper gegebenenfalls mindestens einer weiteren Wärmebehandlung unterworfen werden kann.Permanent magnets or permanent materials made essentially of an alloy of iron (Fe), optionally cobalt (Co), boron (B) and rare earth (SE) sintered, are preferably used when high coercive force, high remanence and / or large Energy product are required. The component forming or containing the magnetic phase of the Se 2 Fe 14 B type, some of the Fe atoms being able to be replaced by Co atoms, is produced and pulverized by melt metallurgy, which powder, optionally mixed with additives, is pressed into a green compact in a magnetic field and this is sintered and the sintered body can optionally be subjected to at least one further heat treatment.
Aus der EP-B1-0126802 sind gesinterte Permanentmagnete des Typs Fe-B-R ( R bedeutet mindestens ein SE-Element einschließlich Y) bekannt geworden, bei welchen Fe teilweise durch Co ersetzt werden kann. Die Elemente sind dabei auf Grund des verwendeten Herstellverfahrens in der magnetischen Phase homogen verteilt und eine Wärme- oder Alterungsbehandlung des Sinterkörpers soll die magnetischen Werte verbessern. Wird Fe teilweise durch Co ersetzt, so erfolgt dadurch eine Erhöhung des Curie-Punktes bzw. der Curie-Temperatur (Tc) des Magnetwerkstoffes, dessen Koerzitivkraft, wie dem Fachmann bekannt ist, jedoch mit steigendem Co-Gehalt sinkt, wodurch auch das Energieprodukt nachteilig beeinflußt werden kann.From EP-B1-0126802 sintered permanent magnets of the Fe-B-R type (R means at least one SE element including Y) have become known, in which Fe can be partially replaced by Co. The elements are homogeneously distributed in the magnetic phase due to the manufacturing process used, and a heat or aging treatment of the sintered body is said to improve the magnetic values. If Fe is partially replaced by Co, this increases the Curie point or the Curie temperature (Tc) of the magnetic material, the coercive force of which, as is known to the person skilled in the art, however decreases with increasing Co content, which also adversely affects the energy product can be influenced.
Um Permanentmagnete mit verbesserten magnetischen Eigenschaften bei Raumtemperatur zu schaffen, wird gemäß EP-B1-0102552 vorgeschlagen, eine Co-freie Legierung mit einem Gehalt an Fe-B-R einzusetzen, die mindestens eine stabile Verbindung des ternären Systems Fe-B-R enthält, wobei R mindestens ein Seltenerdenelement einschließlich Yttrium bedeutet. Die magnetiche Hauptphase muß dabei eine intermetallische Verbindung mit konstanter Zusammensetzung sein, was eine homogene Verteilung der Legierungselemente bedingt. Abgesehen von dem großen legierungstechnischen Aufwand bei der Fertigung der Ausgangslegierung und den starken Streuungen der magnetischen Werte des sintertechnisch hergestellten Magnetwerkstoffes weist dieser eine signifikante Abnahme der magnetischen Kennwerte mit steigender Temperatur im Bereich von Raumtemperatur bis 200 ° C auf, wobei der Curie-Punkt schon bei etwa 300 °C erreicht wird.In order to create permanent magnets with improved magnetic properties at room temperature, one is proposed according to EP-B1-0102552 Use Co-free alloy containing Fe-BR, which contains at least one stable compound of the ternary system Fe-BR, where R means at least one rare earth element including yttrium. The main magnetic phase must be an intermetallic compound with a constant composition, which requires a homogeneous distribution of the alloy elements. In addition to the great expenditure on alloy technology in the production of the starting alloy and the strong scatter of the magnetic values of the sintered magnetic material, this shows a significant decrease in the magnetic characteristics with increasing temperature in the range from room temperature to 200 ° C, the Curie point already at about 300 ° C is reached.
Ferner ist aus der EP-A1-0265006 ein Verfahren zur Herstellung von gesinterten Permanentmagneten bekannt, bei welchem stöchiometrisch zusammengesetztes kristallines RE2(FeCo)14B -Material ( RE bedeutet Seltene Erden) mit einem anderen Material gemahlen wird, wobei dieses andere Material beim Sinterprozeß eine zweite nicht magnetische Phase an der Oberfläche der magnetischen Körner aus RE2(FeCo)14B bildet. Damit soll erreicht werden, daß die genaue chemische Zusammensetzung bei homogener Verteilung aller Elemente der magnetischen Phase im Magnetwerkstoff unabhängig von der zweiten paramagnetischen Phase, die besondere schmelztechnische Eigenschaften und/oder Zusammensetzungen aufweisen kann, einstellbar ist. Bei dieser Ausführungsform besteht jedoch der Nachteil im großen legierungstechnischen Aufwand und der schlechten Reproduzierbarkeit der magnetischen Werkstoffdaten.Furthermore, from EP-A1-0265006 a process for the production of sintered permanent magnets is known, in which stoichiometrically composed crystalline RE 2 (FeCo) 14 B material (RE means rare earths) is ground with another material, this other material being used in Sintering process forms a second non-magnetic phase on the surface of the magnetic grains made of RE 2 (FeCo) 14 B. This is intended to ensure that the exact chemical composition can be set independently of the second paramagnetic phase, which can have special melting properties and / or compositions, with a homogeneous distribution of all elements of the magnetic phase in the magnetic material. In this embodiment, however, there is a disadvantage in the high expenditure on alloy technology and the poor reproducibility of the magnetic material data.
Ein SE-Fe-B- Permanentmagnetwerkstoff, bei welchem im wesentlichen an den Korngrenzen der Körner, die aus einer magnetischen Phase gebildet sind, ein Legierungszusatz enthaltend ein Element aus der Gruppe der Schweren SE und/oder SSE-Verbindungen, gegebenenfalls mit Korngrenzenzusätzen, angelagert ist, ist durch EP-A-0395625 offenbart.An SE-Fe-B permanent magnet material in which an alloy additive containing an element from the group of the heavy SE and / or SSE compounds, optionally with grain boundary additives, is added to the grain boundaries of the grains, which are formed from a magnetic phase is disclosed by EP-A-0395625.
Aus der WO-A-8902156 ist ein Sintermagnet bekannt, dessen Gefüge frei von großen Fe4NdB4- Körnern ist und dessen Zusammensetzung derart gewählt ist, daß der Werkstoff bei Sintertemperatur im Zweiphasengebiet und zwar in einer hartmagnetischen Phase und einer Nd-reichen Phase liegt.A sintered magnet is known from WO-A-8902156, the structure of which is free of large Fe 4 NdB 4 grains and the composition of which is selected such that the material at sintering temperature is in a two-phase area, namely in a hard magnetic phase and an Nd-rich phase.
Die EP-A-0425469 bezieht sich auf einen gesinterten SE-Fe-B-Permanentmagnet(werkstoff), bei welchem im wesentlichen an den Korngrenzen der magnetischen Phase die örtliche Konzentration des SE-Gehaltes ansteigt, daß also über den Kornquerschnitt eine inhomogene Verteilung des SE-Gehaltes gegeben ist.EP-A-0425469 relates to a sintered SE-Fe-B permanent magnet (material) in which the local concentration of the SE content increases essentially at the grain boundaries of the magnetic phase, that is to say that an inhomogeneous distribution of the SE content is given.
In den Patent Abstracts of Japan Vol. 12 No. 165 ( C-496)3012 May 18, 1988, JP-62274046 ist ein Permanentmagnet offenbart, der aus einer gesinterten Pulvermischung, welche aus mindestens zwei Pulverarten gebildet ist, besteht. Dabei wird ein Pulver bestehend aus Nd2Fe14B6, also einer hartmagnetischen Phase, mit einer pulverisierten paramagnetischen Legierung aus Nd95Fe5 und/oder Nd15F77 B8 und/oder Nd2FeB16 und/oder Nd2 Fe7B6 gemischt. Im Hinblick auf eine Herstellung von kleineren und leistungsfähigeren Geräten, die mit Permanentmagneten bestückt sind, besteht der Wunsch, deren magnetische Kennwerte zu erhöhen und zu stabilisieren.In Patent Abstracts of Japan Vol. 12 No. 165 (C-496) 3012 May 18, 1988, JP-62274046 a permanent magnet is disclosed which consists of a sintered powder mixture which is formed from at least two types of powder. A powder consisting of Nd 2 Fe 14 B 6 , i.e. a hard magnetic phase, with a powdered paramagnetic alloy of Nd 95 Fe 5 and / or Nd 15 F 77 B 8 and / or Nd 2 FeB 16 and / or Nd 2 Fe 7 B 6 mixed. With regard to the manufacture of smaller and more powerful devices that are equipped with permanent magnets, there is a desire to increase and stabilize their magnetic characteristics.
Der Erfindung liegt die Aufgabe zugrunde, die Nachteile der bekannten SE,(FeCo),B - enthaltenden Magnete(-werkstoffe) sowie ihrer Herstellverfahren zu beseitigen und gesinterte Permanentmagnete anzugeben sowie zu erstellen, die hohe Sättigungsmagnetisierung, hohe Koerzitivkraft und hohes Energieprodukt bei guter Temperaturstabilität und hohem Curie-Punkt bei geringen Herstellkosten aufweisen. Ein weiteres Ziel der Erfindung ist, die Höhe des Curie-Punktes der Permanentmagnete(-werkstoffe) den Anforderungen entsprechend auf einfache Weise einstellbar zu machen.The invention has for its object to eliminate the disadvantages of the known SE, (FeCo), B - containing magnets (materials) and their manufacturing processes and to specify and create sintered permanent magnets, the high saturation magnetization, high coercive force and high energy product with good temperature stability and have a high Curie point at low manufacturing costs. Another object of the invention is to make the height of the Curie point of the permanent magnets (materials) easily adjustable according to the requirements.
Diese Aufgabe wird bei einem Permanentmagnet(-werkstoff) der eingangs genannten Art durch die kennzeichnenden Merkmale des Anspruchs 1 gelöst. Vorteilhafte Weiterbildungen sind in den Unteransprüchen gekennzeichnet.This object is achieved in a permanent magnet (material) of the type mentioned by the characterizing features of claim 1. Advantageous further developments are characterized in the subclaims.
Beim erfindungsgemäßen Permanentmagnet(-werkstoff) werden synergetisch eine Reihe von Vorteilen erreicht, wobei nachteilige Wechselwirkungen von einzelnen Maßnahmen weitgehend unterdrückt sind und die Gesamtheit der magnetischen Eigenschaften wesentlich erhöht wird. Die wissenschaftlichen Grundlagen und Ursachen dieser Kombinationseffekte sind noch nicht vollkommen geklärt; es handelt sich jedoch im wesentlichen dabei um physikalisch-chemische Wirkungen in Verbindung mit der Magnetokinetik.In the permanent magnet (material) according to the invention, synergistically A number of advantages are achieved, disadvantageous interactions of individual measures being largely suppressed and the totality of the magnetic properties being significantly increased. The scientific basis and causes of these combination effects have not yet been fully clarified; however, these are essentially physico-chemical effects in connection with magnetokinetics.
Beim erfindungsgemäßen Permanentmagnet(-werkstoff) wird der hartmagnetische Anteil aus mehreren magnetischen Phasen gebildet, die, wie sich völlig überraschend gezeigt hat, in vorteilhafter Wechselwirkung zueinander stehen. Wichtig dabei ist, daß eine oder mehrere magnetische Phasen als Zentralphase oder Kernphase aus oberflächengeglätteten bzw. diffusionseingeformten Körnern gebildet ist, wobei nach neuesten Erkenntnissen durch Diffusion ein oberflächliches Umkristallisieren erfolgen kann und ein weiterer magnetischer Phasenanteil sich orientiert als Peripherphase an die Zentralphase anlagert bzw. dieser zuordnet. Dadurch kann ein hoher Anteil an magnetischem Volumen im Werkstoff erreicht und eine Domänwandbildung und/oder Domänwandverschiebung vermindert werden, wodurch eine Vergrößerung der Koerzitivkraft und in der Folge des Energieproduktes eintritt. Die paramagnetische Zwischen- oder Bindephase soll eine höhere Konzentration an SE als die magnetischen Phasen und gegebenenfalls Einlagerungen und/oder Zusätze aufweisen, wodurch eine weitere Blockierung von Domänwänden bewerkstelligt wird. Besondere magnetische Eigenschaften des Werkstoffes werden erreicht, wenn die Körner der Zentral- oder Kernphase einen Durchmesser von 10 bis 100 µm aufweisen und um die Körner die magnetische Peripherphase oder Phasen schalenartig angelagert ist oder sind.In the permanent magnet (material) according to the invention, the hard magnetic component is formed from a plurality of magnetic phases which, as has been shown completely surprisingly, interact advantageously with one another. It is important here that one or more magnetic phases as the central phase or core phase are formed from surface-smoothed or diffusion-molded grains, whereby according to the latest findings, surface recrystallization can take place by diffusion and a further magnetic phase component is oriented towards the central phase as a peripheral phase or is attached to it assigns. As a result, a high proportion of magnetic volume in the material can be achieved and domain wall formation and / or domain wall displacement can be reduced, as a result of which an increase in the coercive force and consequently in the energy product occurs. The paramagnetic intermediate or binding phase should have a higher concentration of SE than the magnetic phases and, if appropriate, inclusions and / or additives, as a result of which a further blocking of domain walls is accomplished. Special magnetic properties of the material are achieved if the grains of the central or core phase have a diameter of 10 to 100 μm and the magnetic peripheral phase or phases are or are attached to the grains in a shell-like manner.
Wenn zwei oder gegebenenfalls mehrere magnetische Phasen unterschiedliche SE-Elemente und/oder Co-Konzentrationen besitzen und insbesondere zumindest eine Zentral- oder Kemphase einen höheren Co-Gehalt aufweist, so wird synergetisch ein hoher Sättigungsmagnetismus bei hoher Koerzitivkraft des Permanentmagneten erreicht werden. Gute magnetische Stabilität bei hohen magnetischen Kennwerten werden erhalten, wenn die örtliche Co-Konzentration an den Korngrenzen bzw. im Korngrenzenbereich zwischen Phasen mit unterschiedlichem Co-Gehalt diffusionskinetisch gebildete Übergänge, das bedeutet einen überproportionalen Anstieg vom niedrigen Niveau mit einer anschließenden asymptotischen Angleichung an ein höheres Niveau, aufweist. Trotz orientierter Anlagerung zwischen zwei magnetischen Phasen wird wahrscheinlich auf Grund der unterschiedlichen Austauschkopplung der magnetischen Momente durch den diffusionskinetisch gebildeten Übergang der Co-Konzentration im Grenzenbereich eine für Domänwände wirkende energetische Barriere gebildet.If two or possibly several magnetic phases have different RE elements and / or Co concentrations and in particular at least one central or core phase has a higher Co content, a high saturation magnetism with high coercive force of the permanent magnet will be achieved synergistically. Good magnetic stability with high magnetic parameters are obtained if the local Co concentration at the grain boundaries or in the grain boundary area between phases with different Co content, that is to say transitions formed by diffusion kinetics shows a disproportionate increase from the low level with a subsequent asymptotic adjustment to a higher level. Despite oriented attachment between two magnetic phases, an energetic barrier for domain walls is likely to be formed due to the different exchange coupling of the magnetic moments through the diffusion kinetic transition of the Co concentration in the border area.
Wenn gemäß einer bevorzugten Form der SE-Anteil in den magnetischen Phasen im wesentlichen durch Leichte Seltene Erden ( LSE), insbesondere Nd, gebildet ist und der SE-Anteil in der Zwischen- oder Bindephase Schwere Seltene Erden (SSE) enthält, werden besonders hohe magnetische Kennwerte des Magneten erreicht. Die Erfindung betrifft femer ein Verfahren zur Herstellung von Seltene Erden ( SE) enthaltendem(n), magnetisch ausgerichtetem(n), gesintertem(n) Permanentmagneten(en)(-werkstoffen) gemäß Anspruch 1, dessen ( deren) Grundwerkstoff bzw. Ausgangsmaterial schmelzmetallurgisch hergestellt ist, wobei dieser bzw. dieses im wesentlichen zu Pulver zerkleinert, mit Zusätzen gemischt, zu einem Grünling gepreßt und der Grünling gesintert sowie geglüht wird. Erfindungsgemäß ist ein derartiges Verfahren durch die kennzeichnenden Merkmale des Anspruchs 8 bezeichnet.If, according to a preferred form, the RE portion in the magnetic phases is essentially formed by light rare earths (LSE), in particular Nd, and the RE portion in the intermediate or binding phase contains heavy rare earths (SSE), particularly high levels become Magnetic characteristics of the magnet reached. The invention further relates to a method for producing rare earth (SE) containing (s), magnetically aligned (s), sintered (s) permanent magnet (s) according to claim 1, its base material or starting material by melt metallurgy is produced, this or this is essentially ground into powder, mixed with additives, pressed into a green body and the green body is sintered and annealed. According to the invention, such a method is characterized by the characterizing features of claim 8.
Die Vorteile der Erfindung bestehen insbesondere darin, daß mindestens zwei magnetische Phasen bildende Grundwerkstoffe bzw. Ausgangsmaterialien mit unterschiedlichen chemischen Zusammensetzungen und daher unterschiedlichen magnetischen Eigenschaften hergestellt, zu Pulver zerkleinert und vermengt werden, wodurch eine die magnetischen Kennwerte günstig beeinflussende Wechselwirkung der Grundwerkstoffe erreicht werden kann. Die Zerkleinerung eines Grundwerkstoffes erfolgt dabei zu Pulver mit geringeren Teilchengrößen bzw. zu Feinpulver, welches bei der Sinterung des unter Magnetfeldausrichtung gepreßten Grünlings eine frühere Erweichung bzw. Plastizität zeigt und einen besonders guten Kontakt zu den Teilchen bzw. Körnern des Grobpulvers herstellt. Dies ist für de Wirkung der Diffusionsbehandlung bzw.- glühung, wobei die Phasengrenzen entsprechend günstig ausgebildet werden, wichtig.The advantages of the invention consist in particular in that at least two magnetic phase-forming base materials or starting materials with different chemical compositions and therefore different magnetic properties are produced, comminuted into powders and mixed, as a result of which an interaction of the base materials which has a favorable influence on the magnetic characteristics can be achieved. A basic material is comminuted to powder with smaller particle sizes or to fine powder, which shows an earlier softening or plasticity during the sintering of the green compact pressed under magnetic field alignment and produces particularly good contact with the particles or grains of the coarse powder. This is important for the effect of the diffusion treatment or annealing, the phase boundaries being designed to be correspondingly favorable.
Insbesondere im Hinblick auf eine Oxidation bei der Zerkleinerung hat es sich als vorteilhaft herausgestellt, wenn die SE-Konzentration der Grundwerkstoffe höher bemessen wird als diejenige der magnetischen Phase vom Typ SE2(FeCo)14B, wobei , wie gefunden wurde, die Zusammensetzungen SE16(FeCo)77B7, SE15(Feco)77B8 und SE14(FeCo)80B6 besonders gute Eignung aufweisen. Ist zumindest ein Grundwerkstoff mit Co legiert und der Eisenanteil der magnetischen Phase bis zu 40 % durch Co substituiert, so sind besonders gute Temperaturstabilität und hohe Curie-Temperaturen der Magnete erreichbar.Particularly with regard to oxidation during grinding, it has proven to be it is found to be advantageous if the SE concentration of the base materials is dimensioned higher than that of the magnetic phase of type SE 2 (FeCo) 14 B, the compositions SE 16 (FeCo) 77 B 7 , SE 15 (Feco) having been found. 77 B 8 and SE 14 (FeCo) 80 B 6 are particularly suitable. If at least one base material is alloyed with Co and the iron portion of the magnetic phase is substituted by up to 40% with Co, particularly good temperature stability and high Curie temperatures of the magnets can be achieved.
Wenn weiters, wie in günstiger Weise vorgesehen, der SE-Anteil der Grundwerkstoffe im wesentlichen durch LSE gebildet wird, sind die Remanenz und das Energieprodukt erhöht. Im Sinne besonders guter magnetischer Kennwerte hat es sich als günstig erwiesen, wenn ein oder mehrere Grundwerkstoffe zu Grobpulver mit einem Komdurchmesser von 10 bis 100 µm, vorzugsweise von 10 bis 60 µm, insbesondere von 15 bis 30 µm, zerkleinert werden und mindestens ein weiterer Grundwerkstoff zu Feinpulver mit einem Teilchendurchmesser von 0,5 bis 8 µm, insbesondere von 3 bis 8 µm, gemahlen wird, wobei unterschiedliche Co-Gehalte im Grob- und Feinpulver die magnetischen Kennwerte weiters verbessern.If, moreover, as provided in a favorable manner, the SE portion of the base materials is essentially formed by LSE, the remanence and the energy product are increased. In the sense of particularly good magnetic characteristics, it has proven to be advantageous if one or more base materials are comminuted into coarse powder with a grain diameter of 10 to 100 μm, preferably 10 to 60 μm, in particular 15 to 30 μm, and at least one further base material is ground to fine powder with a particle diameter of 0.5 to 8 µm, in particular from 3 to 8 µm, different co-contents in the coarse and fine powder further improving the magnetic characteristics.
Wenn gemäß einer bevorzugten Form als Zusätze zu den Pulvern Verbindungen von SSE, wie beispielsweise Dy2O3 und/oder Boride, z.B. Fe2B, und/oder Metalle, z.B. Al, und /oder Oxide, z.B. Al2O3 und/oder SE- Oxide eingebracht, insbesondere die Pulver mit diesen Stoffen mechanisch legiert werden, werden eine Domänwandbildung und eine Domänwandverschiebung weiter vermindert und höhere Koerzitivkräfte erreicht.If according to a preferred form, as additives to the powders, compounds of SSE, such as, for example, Dy 2 O 3 and / or borides, for example Fe 2 B, and / or metals, for example Al, and / or oxides, for example A 12 O 3 and / or SE oxides are introduced, in particular the powders are mechanically alloyed with these substances, domain wall formation and domain wall displacement are further reduced and higher coercive forces are achieved.
Ein besonders wichtiges Kennzeichen der Erfindung ist eine Diffusionsbehandlung des gesinterten Magnet(en)(-werkstoffes), welche vorteilhaft bei einer Temperatur unterhalb der Sintertemperatur und günstigerweise im Pendelglühverfahren erfolgt, weil dabei eine Glättung der Komoberflächen des Grobpulvers erfolgt und an den geglätteten Kornoberflächen mikrostrukturorientiert eine im wesentlichen schalige Anlagerung der vom Feinpulver gebildeten Phase bewirkt wird, was eine wesentliche Verbesserung der magnetischen Kennwerte erbringt.A particularly important feature of the invention is a diffusion treatment of the sintered magnet (s) (material), which is advantageously carried out at a temperature below the sintering temperature and expediently in the pendulum annealing process, because the grain surfaces of the coarse powder are smoothed and a microstructure-oriented on the smoothed grain surfaces essentially shell-like accumulation of the phase formed by the fine powder is brought about, which brings about a significant improvement in the magnetic characteristics.
Fertigungstechnisch, jedoch auch im Hinblick auf besondere magnetische Einzelwerte, kann es weiters günstig sein, wenn Pulver mit bestimmten Zusammensetzungen, insbesondere Co-Gehalten, anteilsmäßig vermengt werden. Auf einfache Weise und besonders wirtschaftlich sind dadurch Permanentmagnete mit für bestimmte Anwendungen bzw. Anforderungen besonders ausgebildeten magnetischen Einzelwerten herstellbar.In terms of production technology, but also with regard to particular magnetic individual values, it can furthermore be advantageous if powders with certain compositions, in particular co-contents, are proportionally mixed. Permanent magnets with individual magnetic values specially designed for specific applications or requirements can thus be produced in a simple and particularly economical manner.
Aus den Zeichnungen kann die Erfindung beispielsweise ersehen werden. Es zeigen Fig.1 und Fig. 2 schematisch den Ablauf der erfindungsgemäßen Herstellung von Permanentmagnetwerkstoffen.The invention can be seen, for example, from the drawings. 1 and 2 show schematically the sequence of manufacture of permanent magnet materials according to the invention.
Im folgenden wird die Erfindung anhand von beiliegenden Tabellen 1,2,3a und 3b, in welchen Legierungsgehalte und Mittelwerte von magnetischen Messungen von Permanentmagnetkörpern angegeben sind, weiter erläutert.
In Tabelle 1 sind Zusammensetzungen der Grundwerkstoffe mit stöchiometrischen Parametern bezeichnet.
In Tabelle 2 sind mit der Bezeichnung V1 bis V7 die Zusammensetzungen und die magnetischen Kennwerte von Vergleichsmagneten(-werkstoffen) angegeben. In Tabelle 3a und 3b unter den Nummern 1 bis 23 werden erfindungsgemäße Permanentmagnet(-werkstoffe) angeführt.
Wie aus den Mittelwerten der magnetischen Messungen hervorgeht, werden bei den erfindungsgemäßen Permanentmagneten durch den Aufbau mit mehreren unterschiedlich zusammengesetzten magnetischen Phasen mit diffusionseingeformten Körnern und Anlagerungen hohe magnetische Kennwerte bei erhöhter Curie-Temperatur erreicht. Die Wechselwirkung der mikrostrukturorientiert aneinander angelagerten oder einander zugeordneten dmagnetischen Phasen führt dabei synergetisch, im Vergleich mit üblichen SE-Permanentmagneten, zu verbesserten magnetischen Eigenschaften.
Table 1 shows compositions of the base materials with stoichiometric parameters.
Table 2 shows the compositions and the magnetic characteristics of reference magnets (materials) with the designation V1 to V7. Tables 3a and 3b under numbers 1 to 23 list permanent magnets (materials) according to the invention.
As can be seen from the mean values of the magnetic measurements, in the permanent magnets according to the invention, high magnetic characteristics at an elevated Curie temperature are achieved by the construction with a plurality of differently composed magnetic phases with diffusion molded grains and deposits. The interaction of the microstructure-oriented attached or assigned magnetic phases synergistically leads to improved magnetic properties in comparison with conventional SE permanent magnets.
Claims (17)
- A permanent-magnet material or a sintered permanent magnet, containing 8 to 30 atom % rare earths (RE), 2 to 28 atom % boron (B) and the remainder iron (Fe) or iron and cobalt (Co) and having a hard magnetic proportion or o hard magnetic phase of the Se2Fe14B type, wherein some of the Fe atoms can be replaced by Co atoms, characterised in that the hard magnetic proportion is at least 65 vol.% and this hard magnetic proportion comprises at least two hard magnetic phases with different chemical compositions, at least one hard magnetic phase in the sintered structure being formed from smooth-surfaced, relatively coarse grains as a central phase, to which at least one further hard magnetic phase is attached as o peripheral phase, the paramagnetic binder phase(s) - connecting the hard magnetic phase components - of the sintered structure having a higher concentration of RE in comparison with the hard magnetic phases.
- A permanent-magnet material or a sintered permanent magnet according to claim 1, characterised in that the smooth-surfaced grains of the hard magnetic central phase(s) have a diameter of 10 to 100 µm, preferably 10 to 60 µm, in particular 15 to 30 µm.
- A permanent-magnet material or a sintered permanent magnet according to claim 1 or 2, characterised in that the hard magnetic peripheral phase(s) are substantially attached to the smooth-surfaced grain boundaries of the hard magnetic central phase(s), in particular in a scale-like manner.
- A permanent-magnet material or a sintered permanent magnet according to any one of claims 1 to 3, characterised in that the hard magnetic central phase(s) and/or the hard magnetic peripheral phase(s) have different RE elements and/or different Co concentrations.
- A permanent-magnet material or a sintered permanent magnet according to any one of claims 1 to 4, characterised in that at least one hard magnetic central phase has a higher Co concentration than the hard magnetic peripheral phase(s) which is (are) preferably low in Co or Co-free.
- A permanent-magnet material or a sintered permanent magnet according to any one of claims 1 to 5, characterised in that the local Co concentrations at the grain boundaries or in the grain-boundary region between phases with different Co contents have abrupt transitions formed by diffusion kinetics.
- A permanent-magnet material or a sintered permanent magnet according to any one of claims 1 to 6, characterised in that the RE proportion in the hard magnetic phases is substantially formed by light rare earths (LRE), in particular Nd, and the RE proportion in the binder phase(s), which can have additions of borides and/or oxides and/or metals, substantially contains heavy rare earths (HRE), in particular Dy.
- A process for the production of rare-earth-containing, magnetically aligned, sintered permanent magnets, containing 8 to 30 atom % rare earths (RE), 2 to 28 atom % boron (B) and the remainder iron (Fe) or iron and cobalt (Co) and having a hard magnetic proportion or a hard magnetic phase of the Se2Fe14B type, wherein some of the Fe atoms can be replaced by Co atoms, the base material or starting material of the permanent magnets being produced by fusion metallurgy, the said material substantially being pulverised, mixed with additives and pressed into a green compact and the green compact being sintered and annealed to produce sintered permanent magnets according to any one of claims 1 to 7, characterised in that at least two base materials or starting materials are melted and allowed to solidify, at least one base material being provided with a chemical composition different from the other base material and the base materials being pulverised, at least one base material being ground into a powder with substantially smaller particle sizes or grain diameters, whereupon additives are added and the pulverised base materials are mixed, after which the mixture is pressed, as is known per se, into a green compact with magnetic field alignment, the green compact is sintered and the sintered body undergoes annealing treatment to smooth the surface of the grains of the central phase.
- A process according to claim 8, characterised in that the base materials with a higher RE concentration than that corresponding to the magnetic phase of the SE2(Feco)14B type are melted and, in particular, produced with compositions corresponding toRE16(Fe,Co)77B7RE15(Fe,Co)77B8RE14(Fe,Co)80B6where the expression (Fe,Co) represents the Fe component which is optionally partly replaced by Co.
- A process according to claim 8 or 9, characterised in that at least one base material is alloyed with Co and the iron proportion is up to 40% replaced by Co.
- A process according to any one of claims 8 to 10, characterised in that the RE proportion of the base materials is substantially formed by light rare earths (LRE).
- A process according to any one of claims 8 to 11, characterised in that one or more base materials are ground into coarse powder with a particle or grain diameter of 10 to 100 µm, preferably 10 to 60 µm, in particular 15 to 30 µm, and in that at least one further base material is ground into fine powder with a grain diameter of 0.5 to 8 µm, in particular 3 to 8 µm.
- A process according to any one of claims 8 to 12, characterised in that the or at least one base material ground into coarse powder is produced with different RE and/or different Co contents in comparison with the or at least one base material ground into fine powder.
- A process according to any one of claims 8 to 13, characterised in that additives in solid and/or liquid form, e.g. organometallic compounds, are added to the coarse and/or fine powder of the base materials, in particular before or during the preliminary grinding or mixing thereof, and are homogeneously distributed in the powder mixture.
- A process according to claims 8 and 14, characterised in that, as is known per se, compounds of heavy rare earths (HRE) and, optionally, metals, borides, e.g. of iron and/or aluminium, oxides, e.g. Al2O3, or oxides of RE and the like are added to the powdered base material(s) as additives and homogeneously distributed.
- A process according to any one of claims 8. 14 and 15, characterised in that the green compact pressed, with magnetic field alignment, from the homogeneous powder mixture provided with additives is sintered and its surface is subsequently smoothed at a temperature below the sintering temperature, preferably by the oscillation annealing method around this temperature.
- A process according to any one of claims 8 to 16, characterised in that the surfaces of the grains of the coarse powder(s) are smoothed, and the phase formed by the fine powder is attached in a preferably scale-like manner to the smoothed grain surfaces so as to be microstructure-orientated.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT596/91 | 1991-03-18 | ||
| AT0059691A AT399415B (en) | 1991-03-18 | 1991-03-18 | METHOD FOR PRODUCING RARE EARTH-CONTAINING PERMANENT MAGNET (S) (MATERIALS) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0505348A1 EP0505348A1 (en) | 1992-09-23 |
| EP0505348B1 true EP0505348B1 (en) | 1996-10-16 |
Family
ID=3494767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92890055A Expired - Lifetime EP0505348B1 (en) | 1991-03-18 | 1992-03-11 | Permanent magnet material or sintered magnet and fabrication process |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0505348B1 (en) |
| AT (2) | AT399415B (en) |
| CZ (1) | CZ281163B6 (en) |
| DE (1) | DE59207356D1 (en) |
| DK (1) | DK0505348T3 (en) |
| ES (1) | ES2095454T3 (en) |
| GR (1) | GR3022263T3 (en) |
| HU (1) | HU216373B (en) |
| PL (1) | PL293878A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4331563A1 (en) * | 1992-09-18 | 1994-03-24 | Hitachi Metals Ltd | Sintered permanent magnet with good thermal stability - containing defined percentages by weight of specified elements |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3729361A1 (en) * | 1987-09-02 | 1989-03-16 | Max Planck Gesellschaft | OPTIMIZATION OF THE STRUCTURE OF THE FE-ND-B BASE SINTER MAGNET |
| AT393177B (en) * | 1989-04-28 | 1991-08-26 | Boehler Gmbh | PERMANENT MAGNET (MATERIAL) AND METHOD FOR PRODUCING THE SAME |
| AT393178B (en) * | 1989-10-25 | 1991-08-26 | Boehler Gmbh | PERMANENT MAGNET (MATERIAL) AND METHOD FOR PRODUCING THE SAME |
-
1991
- 1991-03-18 AT AT0059691A patent/AT399415B/en not_active IP Right Cessation
-
1992
- 1992-03-11 AT AT92890055T patent/ATE144348T1/en not_active IP Right Cessation
- 1992-03-11 DE DE59207356T patent/DE59207356D1/en not_active Expired - Fee Related
- 1992-03-11 DK DK92890055.4T patent/DK0505348T3/en not_active Application Discontinuation
- 1992-03-11 ES ES92890055T patent/ES2095454T3/en not_active Expired - Lifetime
- 1992-03-11 EP EP92890055A patent/EP0505348B1/en not_active Expired - Lifetime
- 1992-03-16 CZ CS92784A patent/CZ281163B6/en unknown
- 1992-03-17 PL PL29387892A patent/PL293878A1/en unknown
- 1992-03-17 HU HU9200889A patent/HU216373B/en not_active IP Right Cessation
-
1997
- 1997-01-09 GR GR970400032T patent/GR3022263T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AT399415B (en) | 1995-05-26 |
| EP0505348A1 (en) | 1992-09-23 |
| DE59207356D1 (en) | 1996-11-21 |
| DK0505348T3 (en) | 1997-03-24 |
| HU9200889D0 (en) | 1992-05-28 |
| ATA59691A (en) | 1994-09-15 |
| PL293878A1 (en) | 1992-10-19 |
| ES2095454T3 (en) | 1997-02-16 |
| CZ281163B6 (en) | 1996-07-17 |
| GR3022263T3 (en) | 1997-04-30 |
| HUT62341A (en) | 1993-04-28 |
| CZ78492A3 (en) | 1993-12-15 |
| ATE144348T1 (en) | 1996-11-15 |
| HU216373B (en) | 1999-06-28 |
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