EP0505348A1 - 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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- EP0505348A1 EP0505348A1 EP92890055A EP92890055A EP0505348A1 EP 0505348 A1 EP0505348 A1 EP 0505348A1 EP 92890055 A EP92890055 A EP 92890055A EP 92890055 A EP92890055 A EP 92890055A EP 0505348 A1 EP0505348 A1 EP 0505348A1
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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
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- 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).
- SE Rare earths
- B Boron
- Fe remainder iron
- Co iron and cobalt
- Permanent magnets or permanent magnet materials made essentially of an alloy of iron (Fe,) optionally cobalt (Co), boron (B) and rare earths (SE) in the sintering process 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 SE2Fe14B type, some of the Fe atoms being able to be replaced by Co atoms, is produced and pulverized by melt metallurgy, which powder, if appropriate mixed with additives, is pressed into a green compact in the magnetic field and this is sintered and the sintered body can optionally be subjected to at least one further heat treatment.
- EP-A1 0265006 discloses a process for producing sintered permanent magnets, in which stoichiometrically composed crystalline RE2 (FeCo) 14B material (RE means rare earths) is ground with another material, this other material being a second during the sintering process forms non-magnetic phase on the surface of the magnetic grains of Re2 (FeCo) 14B.
- RE means rare earths
- 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) adjustable according to the requirements in a simple manner.
- the hard magnetic component is formed from a plurality of magnetic phases which, as has been found completely surprisingly, interact with one another in an advantageous manner. It is important here that one or more magnetic phases as the central phase or core phase is formed from surface-smoothed or diffusion-molded grains, whereby according to the latest knowledge, a surface recrystallization can take place by diffusion and a further magnetic phase component is oriented towards the central phase or is attached to the central phase assigns. This allows a high proportion of magnetic volume in the material to be achieved Domain wall formation and / or domain wall displacement can be reduced, as a result of which an increase in the coercive force and in the consequence of 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 deposited around the grains in a shell-like manner.
- the SE portion in the magnetic phases is essentially formed by light rare earths (LSE), in particular Nd, and the SE portion in the intermediate or binding phase contains heavy rare earths (SSE) achieved particularly high magnetic characteristics of the magnet
- the invention further relates to a method for producing rare earth (SE) containing (s), magnetically aligned (s), sintered (s) permanent magnet (s) (material (s)), its base material or starting material by melt metallurgy is made. 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 to powder and mixed, whereby an interaction of the base materials which has a favorable influence on the magnetic characteristics can be achieved.
- the crushing of a base material takes place 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 SE2 (FECo) 14B, the compositions SE16 (FECo ) 77B7, SE15 (FeCo) 77B8 and SE14 (FeCo) 80B6 are particularly suitable. If at least one base material is alloyed with Co and the iron portion of the magnetic phase up to 40% is substituted by 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 Dy203 and / or borides, e.g. Fe2B, and / or metals, e.g. Al, and / or oxides, e.g. Al203 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 characteristic 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 advantageously in the pendulum annealing process, because the grains are molded in or the grain surfaces of the coarse powder are smoothed and An essentially shell-like accumulation of the phase formed by the fine powder is brought about on the smoothed grain surfaces in a microstructure-oriented manner, which brings about a significant improvement in the magnetic characteristics.
- s sintered magnet
- FIG. 1 and 2 show schematically the sequence of the manufacture of permanent magnet materials according to the invention.
- Table 1 shows compositions of the base materials with stoichiometric parameters.
- Table 2 shows the composition and the magnetic characteristics of reference magnets (materials) with the designations V 1 to V 7.
- Tables 3a and 3b under numbers 1 to 23 list permanent magnets (materials) according to the invention.
- high magnetic characteristics are achieved at elevated Curie temperature in the permanent magnets according to the invention by the construction with a plurality of differently composed magnetic phases with diffusion molded grains and deposits.
- the interaction of the microstructure-oriented magnetic phases which are attached to one another or assigned to one another synergistically leads to improved magnetic properties in comparison with conventional RE permanent magnets.
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Abstract
Description
Die Erfindung betrifft einen gesintertern Permanentmagnet(-werkstoff) enthaltend 8 bis 30 At.-% Seltene Erden ( SE), 2 bis 28 At.-% Bor (B), Rest Eisen ( Fe) oder Eisen und Kobalt (Co).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).
Permanentmagnete bzw. Permanentmagnetwerkstoffe 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 Magnetfeld zu einem Grünling verpreßt und dieser gesintert wird und der Sinterkörper gegebenenfalls mindestens einer weiteren Wärmebehandlung unterworfen werden kann.Permanent magnets or permanent magnet materials made essentially of an alloy of iron (Fe,) optionally cobalt (Co), boron (B) and rare earths (SE) in the sintering process 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 SE2Fe14B type, some of the Fe atoms being able to be replaced by Co atoms, is produced and pulverized by melt metallurgy, which powder, if appropriate mixed with additives, is pressed into a green compact in the 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-BR type (R means at least one SE element including Y) have become known, in which Fe can be partially replaced by Co. Due to the manufacturing process used, the elements are homogeneously distributed in the magnetic phase and a heat or aging treatment of the sintered body is intended to improve the magnetic values. If Fe is partly replaced by Co, this increases the Curie point or the Curie temperature (Tc) of the magnetic material, the Coercive force, as is known to the person skilled in the art, however, decreases with increasing Co content, as a result of which the energy product can also be adversely affected.
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 magnetische 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, it is proposed according to EP-B1-0102552 to use a Co-free alloy containing Fe-BR, which contains at least one stable compound of the ternary system Fe-BR, where R is at least means a 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 legierungstechnichen Aufwand und der schlechten Reproduzierbarkeit der magnetischen Werkstoffdaten.Furthermore, EP-A1 0265006 discloses a process for producing sintered permanent magnets, in which stoichiometrically composed crystalline RE2 (FeCo) 14B material (RE means rare earths) is ground with another material, this other material being a second during the sintering process forms non-magnetic phase on the surface of the magnetic grains of Re2 (FeCo) 14B. 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.
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) adjustable according to the requirements in a simple manner.
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
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 im Verbindung mit der Magnetokinetik.In the permanent magnet (material) according to the invention, a number of advantages are achieved synergistically, 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 found completely surprisingly, interact with one another in an advantageous manner. It is important here that one or more magnetic phases as the central phase or core phase is formed from surface-smoothed or diffusion-molded grains, whereby according to the latest knowledge, a surface recrystallization can take place by diffusion and a further magnetic phase component is oriented towards the central phase or is attached to the central phase assigns. This allows a high proportion of magnetic volume in the material to be achieved Domain wall formation and / or domain wall displacement can be reduced, as a result of which an increase in the coercive force and in the consequence of 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 deposited around 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 Kernphase 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. in 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 characteristics are obtained if the local Co concentration at the grain boundaries or in the grain boundary area between phases with different Co content is formed by diffusion kinetics, i.e. a disproportionate increase from the low level with a subsequent asymptotic adjustment to a higher one 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 erreichtIf, according to a preferred form, the SE portion in the magnetic phases is essentially formed by light rare earths (LSE), in particular Nd, and the SE portion in the intermediate or binding phase contains heavy rare earths (SSE) achieved particularly high magnetic characteristics of the magnet
Die Erfindung betrifft ferner ein Verfahren zur Herstellung von Seltenen Erden (SE) enthaltendem(n), magnetisch ausgerichtetem(n), gesintertem(n) Permanentmagnet(en) (-werkstoff(en)), dessen (deren) Grundwerkstoff bzw. Ausgangsmaterial schmelzmetallurgisch hergestellt ist.
Erfindungsgemäß ist ein derartiges Verfahren durch die kennzeichnenden Merkmale des Anspruchs 8 bezeichnet.The invention further relates to a method for producing rare earth (SE) containing (s), magnetically aligned (s), sintered (s) permanent magnet (s) (material (s)), its base material or starting material by melt metallurgy is made.
According to the invention, such a method is characterized by the characterizing features of
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 die 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 to powder and mixed, whereby an interaction of the base materials which has a favorable influence on the magnetic characteristics can be achieved. The crushing of a base material takes place 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 substitiert, so sind besonders gute Temperaturstabilität und hohe Curie-Temperaturen der Magnete erreichbar.Particularly with regard to oxidation during comminution, it has proven to be advantageous if the SE concentration of the base materials is dimensioned higher than that of the magnetic phase of type SE2 (FECo) 14B, the compositions SE16 (FECo ) 77B7, SE15 (FeCo) 77B8 and SE14 (FeCo) 80B6 are particularly suitable. If at least one base material is alloyed with Co and the iron portion of the magnetic phase up to 40% is substituted by Co, particularly good temperature stability and high Curie temperatures of the magnets can be achieved.
Wenn weiters 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 Korndurchmesser 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 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 Dy203 und/oder Boride, z.B. Fe2B, und/oder Metalle, z.B. Al, und/oder Oxide, z.B. Al203, 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, compounds of SSE such as Dy203 and / or borides, e.g. Fe2B, and / or metals, e.g. Al, and / or oxides, e.g. Al203 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 Einformung der Körner bzw. eine Glättung der Kornoberflächen 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.
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.A particularly important characteristic 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 advantageously in the pendulum annealing process, because the grains are molded in or the grain surfaces of the coarse powder are smoothed and An essentially shell-like accumulation of the phase formed by the fine powder is brought about on the smoothed grain surfaces in a microstructure-oriented manner, which brings about a significant improvement in the magnetic characteristics.
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 are therefore also simple and particularly economical for certain Applications or requirements of specially designed individual magnetic values can be produced.
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 the 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 V 1 bis V 7 die Zusammensetzung 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 magnetischen Phasen führt dabei synergetisch, im Vergleich mit üblichen SE- Permanentmagneten, zu verbesserten magnetischen Eigenschaften.In the following, the invention is further explained with the aid of the attached tables 1, 2, 3a and 3b, in which alloy contents and mean values of magnetic measurements of permanent magnet bodies are given.
Table 1 shows compositions of the base materials with stoichiometric parameters.
Table 2 shows the composition and the magnetic characteristics of reference magnets (materials) with the
Tables 3a and 3b under
As can be seen from the mean values of the magnetic measurements, high magnetic characteristics are achieved at elevated Curie temperature in the permanent magnets according to the invention by the construction with a plurality of differently composed magnetic phases with diffusion molded grains and deposits. The interaction of the microstructure-oriented magnetic phases which are attached to one another or assigned to one another synergistically leads to improved magnetic properties in comparison with conventional RE permanent magnets.
Claims (18)
SE16(Fe,Co)77B7
SE15(Fe,Co)77B8
SE14(Fe,Co)80B6
hergestellt werden, wobei der Ausdruck ( Fe, Co) den Anteil von Fe, der gegebenenfalls teilweise durch Co sustituiert ist, bedeutet.A method according to claim 8, characterized in that the base materials with a higher SE concentration than that which corresponds to the magnetic phase of type SE2 (FeCo) 14B, melted, in particular with compositions accordingly
SE16 (Fe, Co) 77B7
SE15 (Fe, Co) 77B8
SE14 (Fe, Co) 80B6
are produced, the expression (Fe, Co) meaning the proportion of Fe which is optionally partially substituted by Co.
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 true EP0505348A1 (en) | 1992-09-23 |
EP0505348B1 EP0505348B1 (en) | 1996-10-16 |
Family
ID=3494767
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Application Number | Title | Priority Date | Filing Date |
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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 |
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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) |
Cited By (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 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1989002156A1 (en) * | 1987-09-02 | 1989-03-09 | Max-Planck-Gesellschaft Zur Förderung Der Wissensc | OPTIMIZATION OF THE MICROSTRUCTURE OF SINTERED Fe-Nd-B MAGNETS |
EP0395625A2 (en) * | 1989-04-28 | 1990-10-31 | BÖHLER YBBSTALWERKE Ges.m.b.H. | Process of Manufacturing a Permanent Magnet or Permanent Magnet Material |
EP0425469A2 (en) * | 1989-10-25 | 1991-05-02 | BÖHLER YBBSTALWERKE Ges.m.b.H. | Permanent magnet (material) and production process |
-
1991
- 1991-03-18 AT AT0059691A patent/AT399415B/en not_active IP Right Cessation
-
1992
- 1992-03-11 ES ES92890055T patent/ES2095454T3/en not_active Expired - Lifetime
- 1992-03-11 DK DK92890055.4T patent/DK0505348T3/en not_active Application Discontinuation
- 1992-03-11 DE DE59207356T patent/DE59207356D1/en not_active Expired - Fee Related
- 1992-03-11 EP EP92890055A patent/EP0505348B1/en not_active Expired - Lifetime
- 1992-03-11 AT AT92890055T patent/ATE144348T1/en not_active IP Right Cessation
- 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
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1989002156A1 (en) * | 1987-09-02 | 1989-03-09 | Max-Planck-Gesellschaft Zur Förderung Der Wissensc | OPTIMIZATION OF THE MICROSTRUCTURE OF SINTERED Fe-Nd-B MAGNETS |
EP0395625A2 (en) * | 1989-04-28 | 1990-10-31 | BÖHLER YBBSTALWERKE Ges.m.b.H. | Process of Manufacturing a Permanent Magnet or Permanent Magnet Material |
EP0425469A2 (en) * | 1989-10-25 | 1991-05-02 | BÖHLER YBBSTALWERKE Ges.m.b.H. | Permanent magnet (material) and production process |
Non-Patent Citations (2)
Title |
---|
IEEE TRANSACTIONS ON MAGNETICS. Bd. 22, Nr. 5, September 1986, NEW YORK US Seiten 904 - 909; M.TOKUNAGA ET AL: 'MICROSTRUCTURE OF R-Fe-B SINTERED MAGNET' * |
PATENT ABSTRACTS OF JAPAN vol. 12, no. 165 (C-496)(3012) 18. Mai 1988 & JP-62 274 046 ( INOUE JAPAX RES INC ) 28. November 1987 * |
Cited By (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 |
Also Published As
Publication number | Publication date |
---|---|
HU9200889D0 (en) | 1992-05-28 |
DK0505348T3 (en) | 1997-03-24 |
ATA59691A (en) | 1994-09-15 |
PL293878A1 (en) | 1992-10-19 |
CZ78492A3 (en) | 1993-12-15 |
ES2095454T3 (en) | 1997-02-16 |
CZ281163B6 (en) | 1996-07-17 |
GR3022263T3 (en) | 1997-04-30 |
DE59207356D1 (en) | 1996-11-21 |
ATE144348T1 (en) | 1996-11-15 |
AT399415B (en) | 1995-05-26 |
HUT62341A (en) | 1993-04-28 |
EP0505348B1 (en) | 1996-10-16 |
HU216373B (en) | 1999-06-28 |
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