CN1026534C - Rare earth permanentlymagetic material and its preparation method - Google Patents
Rare earth permanentlymagetic material and its preparation method Download PDFInfo
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- CN1026534C CN1026534C CN 91105453 CN91105453A CN1026534C CN 1026534 C CN1026534 C CN 1026534C CN 91105453 CN91105453 CN 91105453 CN 91105453 A CN91105453 A CN 91105453A CN 1026534 C CN1026534 C CN 1026534C
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Abstract
The present invention relates to a permanent magnetic RE material and a fabrication method thereof. The content of rare earth elements in the permanent magnetic RE material is 1 to 8 at%, the content of metalloid elements which mainly contain B is 10 to 22 at% and the residual content of the permanent magnetic RE material is transition group metal which mainly contain Fe. One or more kinds of other transition group metal elements, such as Zn, Al, Mn, Ni, Ca, Cu, Sn, Ti, Zr, Mf, V, Nb, Ta, Cr, Mo, W, are combined to be added. A melting method, a reduction diffusion method or a reduction fusion method is used for preparing alloy. A rapid quenching method or a mechanical alloying method is used for preparing alloy powder, and a bonding method or a hot pressing method is used for preparing alloy magnetic bodies. Isotropy or anisotropy magnetic bodies can be prepared.
Description
The present invention relates to a kind of rare earth-magnesium-yttrium-transition metal-metalloid series permanent magnetic material, contain extremely low rare earth element in its component, do not contain cobalt, and this preparation methods.
Permanent magnetic material is one of important functional material, has a wide range of applications in the many fields of modern science and technology.The typical permanent magnetic material of Shi Yonging was ferrite, aluminium nickel cobalt, Rare-Earth Cobalt and neodymium iron boron magnetic body in the last few years.Ferrite low price, but its performance is lower, Curie temperature is too low, and by contrast, aluminium nickel cobalt performance is slightly high, but comprises the cobalt greater than 30% in the component by weight, mainly contains samarium and cobalt in the Rare-Earth Cobalt, magnetic property is higher, but costs an arm and a leg.Compare neodymium rather than the relative less samarium that is rich in the ores containing rare earths in the neodymium iron boron magnetic body with Rare-Earth Cobalt, price reduces, and its magnetic property is also high.But in general neodymium iron boron magnetic body, neodymium content is more than 30wt%, the magnet material cost depends mainly on the price of neodymium content, thereby price still seems too high, its Curie temperature seem under relatively (～320 ℃) on the low side in addition, have to add a certain amount of cobalt for improving Curie temperature, this has more improved its cost and price.The scope of application and the consumption of this material still are restricted.Patent EPO264153Al provides with the fusion quench and has produced Fe
79-x-yB
21-aThe method of Ry magnetic material, wherein :-5＜x＜5 ,+1＜y＜+5, R is rare earth element nd and Pr, and preparation condition is to vacuumize back system band bits under the argon filling condition, thereby equipment is complicated, and operation easier is bigger.
The objective of the invention is to propose the preparation method of a kind of rare earth-magnesium-yttrium-transition metal-metalloid series permanent magnetic material, its content of rare earth is compared much lower with general Nd-Fe-B series magnet, can not obtain Curie temperature, than general neodymium iron boron height greater than 510 ℃ with adding cobalt yet.In addition, practical rare earth-magnesium-yttrium-transition metal-metalloid series magnet that multiple preparation method can use with preparation is proposed under higher temperature.Its preparation method characteristics are that the foundry alloy raw material can be used pure rare-earth metals, also can adopt rare earth oxide and rare earth-iron-boron or rare earth fluoride.Alloy band bits can be with the preparation of fusing quick-quenching method in air.
It is cheap to the invention provides a kind of employing material, and the magnet Curie temperature increases substantially, the preparation method is simple, be applicable to the preparation method of rare earth-metalloid-magnesium-yttrium-transition metal permanent magnetic material of the requirement of application element microminiaturizations such as electronics, electrical equipment instrument and meter, slimming.
Rare earth-magnesium-yttrium-transition metal of the present invention-metalloid is the light rare earth that permanent-magnet alloy middle rare earth element comprises y, heavy rare earth element is at interior at least a rare earth element, can also adopt two or more luciums, as the praseodymium neodymium mixed rare-earth, contain the mishmetal of cerium.
For obtaining high remanent magnetism, in the RE permanent magnetic alloy, rare earth element is with Pr, Nd, Y, Ce, praseodymium neodymium mixed rare-earth, and it is main containing the cerium mishmetal, and its content accounts for more than the 80at% of alloy middle rare earth element total content.For improving performance, improve coercive force, with one or more are used in combination with the light rare earth element that is main content in heavy rare earth Gd, Tb, Dy, Ho, Er, Tm, the Yb element.Its content accounts for 0～20at% of rare earth total content.
In the RE permanent magnetic alloy, total rare earth content is 1～8at%, and the low content of rare earth of trying one's best can make material cost reduce, but can make magnet can not get hard magnetic property when total amount of rare earth is lower than 1at%.
Magnesium-yttrium-transition metal mainly is based on low-cost Fe, and its content accounts for the 90at%～100at% of magnesium-yttrium-transition metal.In magnesium-yttrium-transition metal, can be without Co.The Curie temperature of magnet is than general neodymium iron boron magnetic body height.For improving performance mainly is to improve coercive force, adds the compound interpolation of one or more elements among following element: Zn, Al, Mn, Cu, Ga, Sn, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, the W, and adding total amount is 0～10at% of Fe content.Addition surpasses 10at% can make magnet remanent magnetism seriously reduce.
Metalloid element mainly is B, can comprise as elements such as Si, C, P.The scope of boron content is 10～24at% in RE permanent magnetic alloy, and in this alloy system, if B content exceeds the above composition range that limits, magnet then can not get hard magnetic property.
Permanent magnetic material of the present invention can be made by different technology, and main process comprises the preparation of alloy, the preparation of alloy powder.The pure rare-earth metals smelting process is adopted in the preparation of alloy, or is raw material with the reduction-diffusion process or the fusion method that reduces with rare earth oxide, rare earth-iron-boron or rare earth fluoride.The preparation of alloy powder can be adopted the fusing quick-quenching method.The preparation of alloy magnet can be adopted the preparation of mull technique or low temperature and pressure method.Be described further below.
Prepare one of method of alloy, used raw material is the pure rare-earth metals that rare earth element adopts one or more, electrolysis Fe or aforesaid other magnesium-yttrium-transition metal of interpolation trace, pure B or B-Fe alloy.In the above composition range, in vacuum or under inert gas conditions, form alloy behind the raw material weighing and burden by ingot casting after the Medium frequency induction melting.
Also can prepare alloy with reduction-diffusion process, raw material adopts one or more oxides of foregoing rare earth element, determines x, y, z by following reaction equation and according to above-described alloying component
Calculate and batching, wherein R
2O
3Be rare earth oxide, R
2O
3, Fe, B particle size＜200 orders, Ca particle diameter＜5mm.Raw material mix the back under inert gas conditions in 700～1200 ℃ handle 2～8 hours after stove reactant is separated in parting liquid after being chilled to room temperature, reclaim alloy then.
Can also prepare alloy like this, adopting one or more chlorides of foregoing rare earth element or fluoride is raw material, by following reaction equation
And after determining x, y, z value according to the above alloying component, calculate and prepare burden, raw material powder particle size requires same method two, raw material mix the back under inert gas conditions in 700～1000 ℃ handle 1-4 hour after stove be chilled to room temperature, reactant is dropped into parting liquid, reclaim alloy.
The method four for preparing alloy is reduction fusion methods, adopting the chloride or the fluoride of one or more rare earth elements is raw material, press reaction equation (2) batching, after the mixing, at 850 ℃～1400 ℃, the argon gas following processing time of condition of 500～760 torrs is 0.5～2 hour, then cooling, remove the slag phase of natural layering, obtain rare earth alloy.
The preparation method one of alloy powder is as follows, adopt the rare earth alloy of above any method preparation, through with argon gas stream molten alloy being injected in behind the induction melting with rotating speed＞15m/s on atwirl single roller or the two roller water-cooled copper wheel, quench cooled is frozen into＜50 μ m thick strips, handled 5 minutes to 1 hour at 500～800 ℃ again, band mechanical crushing or hydrogenation are caused the broken alloy powder of making, and the powder average grain diameter is 1～15 μ m.What need further specify is that band is manufactured process and can be carried out under the vacuum condition that generally uses at present, also can carry out in air.
The preparation method two of alloy powder is as follows, adopt foregoing rare earth metal powder, magnesium-yttrium-transition metal powder, boron powder or employing rare-earth transiting group metal alloy powder, excessively family's metal-metalloid Bization thing alloy powder is a raw material, powder mean particle sizes＜10 μ m.Prepare burden according to above-described rare earth alloy composition range, mix the back and grind in high energy ball mill, the alloy powder after the grinding was handled 5 minutes to 1 hour at 500～800 ℃.The alloy powder granularity of mechanical alloying gained can be adjusted and be controlled by the raw material powder particle size of allocating into.
The preparation method one of rare earth alloy magnet is as follows, adopts low-melting-point metal such as Zn, Sn, Pb or its alloy powder of the alloy powder adding 1～8wt% of above any method preparation to mix, compression moulding, and briquetting pressure is greater than 3ton/cm
2, when pressure is lower than this value, can not obtain high green density.Pressed compact is cured processing at the melting temperature of low-melting-point metal.Make isotropic magnet like this.When mixed powder is orientated (the orientation field intensity is greater than 3KOc) in magnetic field, can make anisotropy magnet.
The preparation method two of rare earth alloy magnet is as follows, adopts the thermoplastic resin of the alloy powder adding 1～12wt% of above any method preparation, thermosetting resin, addition is lower than 1wt%, the alloy powder adhesion is bad, and addition is higher than 12wt%, and the alloy magnet decreased performance is serious.Forming method can adopt compression moulding, extrusion molding, injection moulding and vacuum impregnation technology, because injection mo(u)lding need add more adhesive, thereby magnetic property is lower, but productivity ratio height, the adhesive that vacuum impregnation technology adds is minimum, and the performance of magnet is the highest in several forming methods.If moulding is to carry out in magnetic field, magnetic field intensity can make anisotropic magnet greater than 3KOe.What be illustrated in addition is, because alloy middle rare earth content is low, alloy powder does not need to resemble powder cladding preliminary treatment the alloyed powder of high rare-earth content with anti-oxidation before moulding.
The invention has the advantages that the raw material source is abundant, the preparation method is simple, is easy to suitability for industrialized production.
Example 1 is raw materials used to be Pr, Nd mishmetal, total content 99%, and wherein Pr content 9%.Armco iron, the B-Fe alloy is pressed empirical formula (Pr, Nd)
4Fe
80B
16Batching, in intermediate frequency furnace, under the argon gas condition, be smelted into rare earth alloy, induction melting on chilling facility again is injected in molten alloy on single roller water-cooled copper wheel with the 40m/s high speed rotating with argon gas stream, makes 20 μ m thick strips in air, band was handled 15 minutes at 700 ℃, the band mechanical crushing is become less than 320 purpose powder again, add the thermosetting epoxy resin powder of 5wt% in alloy powder, mixed-powder is orientated under 3KOe magnetic field and in 3ton/cm
2Pressure under compression moulding, pressed compact solidifies down at 200 ℃.Gained magnet performance Br=7KG, iHc=3.6KOe, (BH)
m=7.5MGOe, Tc=514 ℃.
Example 2 is raw materials used to be, neodymium chloride, iron powder, B-Fe powder, metal Ca grain, and Ca grain average grain diameter is less than 5mm, all the other material powder particle mean sizes＜200 orders.The rare earth alloy of preparation is pressed Nd in the reaction equation (2)
xFe
yB
zDetermine x=4.5, y=78, z=17.5 batching is mixed the back and is applied magnetic field and stir being warming up to 1400 ℃ after 0.5 hour in 850 ℃ of insulations under the argon gas condition, be incubated after 15 minutes and cools off, and removes the byproduct of reaction CaCl of natural layering
2, obtain rare earth alloy.Alloy pulverizing process such as example 1.Alloy powder is orientated under 3KOe magnetic field, and is 5ton/cm through pressure
2Compression moulding, be placed on then in the vacuum impregnation plant, be evacuated to 10 earlier
-3Add liquid thermosetting epoxy resin behind the torr, 200 ℃ of curing, the gained magnet performance is Br=7.8KG with the pressed compact behind the dipping, iHc=3.8KOe, (BH)
m=8MGOe.
Example 3 alloying components are (Nd
0.95Dy
0.05)
4Fe
79B
17The preparation method of alloy and alloy powder is with example 1, alloy powder average grain diameter 6 μ m.Adding the 3wt%Zn powder in the alloy powder evenly is orientated pre-molding (pressure is 1ton/cm in the back in magnetic field intensity is the magnetic field of 3KOe
2).Pressed compact is again at 450 ℃ of hot pressing (pressure 5ton/cm
2).The gained magnet performance is Br=7.4KG, iHc=4.2KOe, (BH)
m=7.8MGOe.
Claims (6)
1, a kind of preparation method of permanent magnetic material of low content of rare earth is characterized in that: alloy composition is one or more rare earth elements that 1-8at% comprises Y, the boron of 10-24at%, and surplus is transiting group metal elements based on iron; The preparation of alloy adopts the melting of simple metal raw material to form or adopt rare earth oxide, rare earth-iron-boron or rare earth fluoride to carry out with reduction-diffusion process or reduction fusion method; The preparation of alloy powder is with the fusing quick-quenching method alloy to be made band in air, and causes broken method with mechanical crushing method or hydrogenation at 500-800 ℃ after handling 5 minutes to 1 hour and make.
2, according to the permanent magnetic material preparation method of claim 1, it is characterized in that the alloy preparation: one or more oxides with rare earth element are raw material, press reaction equation
Handled 2-8 hour at 700-1200 ℃.
3, according to the permanent magnetic material preparation method of claim 1, it is characterized in that the alloy preparation: one or more chlorides or fluoride with rare earth element are raw material, press reaction equation
At the 700-1000 ℃ of amount of locating 1-4 hour.
4, according to the permanent magnetic material preparation method of claim 3, it is characterized in that the alloy preparation: press reaction equation (A) batching,, handled 0.5-2 hour in the argon gas of 500-700 torr at 850-1400 ℃.
5, according to the permanent magnetic material preparation method of claim 1, it is characterized in that: described rare earth element is based on Pr, Nd, Y, Ce, praseodymium neodymium mixed rare-earth or contain the cerium mishmetal, its content accounts for more than the 80at% of alloy middle rare earth total amount, all the other are among heavy rare earth Gd, Tb, Dy, Ho, the Er one or more, and content accounts for the 0-20at% of rare earth total content.
6, according to the permanent magnetic material preparation method of claim 1, it is characterized in that: transiting group metal elements is based on iron, one or more elements compounding interpolations among column element: Zn, Al, Mn, Cu, Ga, Sn, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, the W under adding, adding total amount is the 0-10at% of Fe content.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91105453 CN1026534C (en) | 1991-08-10 | 1991-08-10 | Rare earth permanentlymagetic material and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91105453 CN1026534C (en) | 1991-08-10 | 1991-08-10 | Rare earth permanentlymagetic material and its preparation method |
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| CN1069361A CN1069361A (en) | 1993-02-24 |
| CN1026534C true CN1026534C (en) | 1994-11-09 |
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|---|---|---|---|
| CN 91105453 Expired - Fee Related CN1026534C (en) | 1991-08-10 | 1991-08-10 | Rare earth permanentlymagetic material and its preparation method |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383272C (en) * | 2003-04-22 | 2008-04-23 | 上海大学 | Superfine carbide alloy and mfg method thereof |
| CN108085608A (en) * | 2016-11-23 | 2018-05-29 | 龙岩紫荆创新研究院 | The hot-pressed magnets that a kind of R-B-Ti-Fe alloy powders and preparation method thereof are prepared with the alloy powder |
| CN107134338B (en) * | 2017-05-17 | 2020-06-23 | 成都银磁材料有限公司 | Neodymium-iron-boron bonded magnetic powder compositely added with zinc and gadolinium and preparation method thereof |
| CN112712955B (en) * | 2020-12-23 | 2023-02-17 | 安徽大地熊新材料股份有限公司 | Sintered neodymium-iron-boron magnet and preparation method thereof |
| CN112885550A (en) * | 2021-01-14 | 2021-06-01 | 沈阳新橡树磁性材料有限公司 | Preparation method of high-density cerium-based hot-pressed rare earth magnetic steel |
| CN115206665B (en) * | 2022-09-14 | 2022-12-09 | 宁波科宁达工业有限公司 | Neodymium-iron-boron permanent magnet and preparation method thereof |
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