CN1219301C - Agglutination type composite permanent magnetic material of neodymium, iron, boron and iron base soft magnetic powder and its preparing method - Google Patents
Agglutination type composite permanent magnetic material of neodymium, iron, boron and iron base soft magnetic powder and its preparing method Download PDFInfo
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- CN1219301C CN1219301C CN 03117200 CN03117200A CN1219301C CN 1219301 C CN1219301 C CN 1219301C CN 03117200 CN03117200 CN 03117200 CN 03117200 A CN03117200 A CN 03117200A CN 1219301 C CN1219301 C CN 1219301C
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Abstract
The present invention relates to a bonding type Nd-Fe-B Fe-base soft magnetic powder body composite permanent-magnetic material which is composed of the mixed magnetic powder of Nd-Fe-B and Fe-base soft magnetic powder bodies and high molecular binding agents, wherein the formula (measured by weight percentages) of the mixed magnetic powder and the high molecular binding agents comprises: 95 to 98.5% of the mixed magnetic powder and 1.5 to 5% of the high molecular binding agents. The mixed magnetic powder of the Nd-Fe-B and the Fe-base soft magnetic powder bodies comprises the formula (measured by weight percentages): 10 to 90% of Nd-Fe-B magnetic powder and 10 to 90% of the Fe-base soft magnetic powder bodies. The present invention comprises the following processing steps: (1) preparing the Fe-base soft magnetic powder bodies, wherein rapidly quenching Fe-base materials which are smelted into cast ingots into amorphous thin belts which is crystallized at the crystallization temperature of 400 to 500 DEG C and in the crystallization time of 60 to 150 min, and spherically milling crystallized materials by a vacuum ball mill charged with argon gas; (2) preparing composite permanent-magnetic materials, wherein coating the mixed magnetic powder by silylation and then adding binding agents which are harmoniously mixed with the powder and are pressed and moulded by a presser.
Description
One, technical field
The invention belongs to the binding type permanent magnetic material, particularly two or more the binding electromagnetic material that alloy powder was combined into.
Two, background technology
Japan Patent JP61-284906A has announced the binding type permanent magnetic material that a kind of rare earth permanent magnet alloy powder and ferrite are mutually compound, though this material can obtain certain magnetic property and cost reduces significantly, but have following problem: (1) is in order to prevent corrosion, need on composite permanent-magnetic material, carry out the electrophoretic coating protection, but can not conductivity cause the composite permanent-magnetic material surface can not form evenly complete electrophoresis resin coating owing to ferritic, thereby can not effectively protect very easily oxidized neodymium iron boron; (2) RE permanent magnetic alloy and ferritic temperature coefficient (Br) are all big, cause thermal stability very poor; (3) RE permanent magnetic alloy and ferrite powder proportion differ greatly, and are difficult for mixing, and are difficult to guarantee the stable of magnetic property; (4) if adopt cold pressing forming process, need erose particle, the compact strength of ball-type powder compaction is very low.And the neodymium iron boron powder is a flakey, and ferrite powder is spherical, thereby the density of this kind composite permanent-magnetic material is very low.Commercialization the performance of permanent magnetic material see the following form:
The comparison of binding type composite permanent-magnetic material and binding type ferrite performance
| The magnet title | Br(kGs) | Hcb(koe) | Hcj(koe) | (BH)m(MGOe) | Density(g/cm 3) |
| Sprax14/20p * | 2.5 | 2.186 | 3.141 | 1.57 | 3.5 |
| Neofer25/50p ** | 4.0 | 3.518 | 5.905 | 3.518 | 4.3 |
| Neofer39/60p ** | 4.85 | 3.894 | 7.538 | 4.90 | 4.8 |
*Represent a kind of adhesive iron oxysome trade name
*Represent neodymium iron boron and ferritic binding type composite permanent-magnetic material trade name
Chinese patent ZL94111737.5 has announced a kind of plastics bound type Al-Ni-Co, neodymium iron boron composite permanent-magnetic material, component alnico alloy magnetic in this kind composite permanent-magnetic material, because it contains strategic element cobalt and the fewer nickel of Chinese resource reserve, thereby cause this kind alloy powder price comparison high (existing price is generally about 180RMB/kg), can not effectively reduce the cost of composite permanent-magnetic material.
Three, summary of the invention
The present invention is directed to the deficiency that prior art exists, provide a kind of novel binding type permanent-magnetic composite materials and preparation method thereof, to satisfy needs of society.
Technical scheme of the present invention is: select for use the quite cheap iron-based soft magnetic powder of price as one of component of magnetic to reduce the cost of composite permanent-magnetic material; Not only price is very cheap (is more or less the same with ferrite powder for the iron-based soft magnetic powder; generally about 5RMB/kg); and has good conductivity; thereby also has good electrical conductivity with the made composite permanent-magnetic material of another component NdFeB magnetic powder; can form evenly complete smooth macromolecule resin coating on this kind composite permanent-magnetic material surface; effectively protection neodymium iron boron element greatly improves corrosion resistance.With regard to material itself, the corrosion electrode potential of iron-based powder is more much higher than neodymium iron boron, adds a certain amount of iron-based powder, can improve the built-up magnet corrosion electrode potential on the whole, fundamentally improves the corrosion resistance of built-up magnet.In order to improve the density of composite permanent-magnetic material, start with from the preparation method who changes the iron-based soft magnetic powder, iron elder generation fast quenching is become amorphous state, then amorphous state being carried out crystallization handles, carry out pulverization process at last again, resulting like this iron-based soft magnetic powder is the same with fast quenching neodymium iron boron powder, all is flakey, thereby the composite permanent-magnetic material suppressing out have than higher density, improved comprehensive physical property.
Above-mentioned binding type composite permanent-magnetic material, the prescription of its neodymium iron boron, iron-based soft magnetic powder mixing magnetic and high polymer binder (percentage meter by weight) is:
Mix magnetic 95%～98.5%
High polymer binder 1.5%～5%
High polymer binder can be selected epoxy resin, phenolic resins, metatitanic acid diallyl or the like for use.
The prescription of neodymium iron boron, iron-based soft magnetic powder mixing magnetic (percentage meter by weight) is:
NdFeB magnetic powder 10%～90%
Iron-based soft magnetic powder 10%～90%
In order to improve corrosion resistance, in the composite permanent-magnetic material surface coverage macromolecule resin coating is arranged by electrophoresis equipment, this coating can be through the epoxy coating of modification or the acrylic resin of modification etc.
The processing step for preparing above-mentioned bonding type Nd-Fe-B, iron base soft magnetic powder bluk recombination permanent magnetic material is as follows:
1, preparation iron-based soft magnetic powder
Fast quenching became amorphous thin ribbon after iron was smelted into ingot casting, then amorphous thin ribbon being carried out crystallization handles, 400 ℃～500 ℃ of crystallization temperatures, crystallization time 60min～150min, the material after crystallization ball milling in being filled with the vacuum sphere grinding machine of argon gas promptly was prepared into satisfactory iron-based soft magnetic powder in 20～25 minutes.
2, preparation composite permanent-magnetic material
Iron-based soft magnetic powder and NdFeB magnetic powder are mixed the back coat processing with silane, add then that binding agent and powder mix and pass through press compression moulding, briquetting pressure is 6～10T.
The present invention has following beneficial effect:
1, owing to adopt the iron-based soft magnetic powder as raw material, cost reduces significantly, compares with plastics bound type Al-Ni-Co, neodymium iron boron composite permanent-magnetic material with performance, and cost can reduce about 15%.
2, the corrosion electrode potential of iron-based soft magnetic powder is more much higher than neodymium iron boron, adds a certain amount of iron-based soft magnetic powder, can improve the corrosion electrode potential of composite permanent-magnetic material on the whole, fundamentally improves the corrosion resistance of composite permanent-magnetic material.
3, the preparation method who is adopted makes the iron-based soft magnetic powder be flakey, thus the composite permanent-magnetic material suppressing out have than higher density, help improving comprehensive physical property.
4, have better magnetic properties, magnetic energy product (BH) max can reach 8.3MGoe.
5, production technology is simple, and raw material are easy to obtain, and are convenient to suitability for industrialized production.
The present invention can be widely used in fields such as automobile making, household electrical appliance, small and special electric machine, instrument and meter.
Four, embodiment
Embodiment 1:
The mixing magnetic (see Table one and table two) that 9 kinds of different formulations are arranged in the present embodiment; NdFeB magnetic powder is selected the MQP-B magnetic for use, preparation iron-based soft magnetic powder is selected iron silicon boryl alloy for use, be smelted into and carry out fast quenching behind the ingot casting and obtain amorphous thin ribbon, the crystallization temperature of amorphous thin ribbon is 500 ℃, crystallization time is 1 hour, after the crystallization in being filled with the vacuum sphere grinding machine of argon gas the time of ball milling be 20 minutes; Binding agent is selected epoxy resin for use, and content is 2.5% (percetage by weight), and the content that mixes magnetic is 97.5% (percetage by weight); Different proportion mixing magnetic coats processing with silane, and add epoxy adhesive then and mix, compression moulding on press, briquetting pressure is elected 8T as, and formed body all is the standard specimen of φ 10 * 10mm.
The density of the composite permanent-magnetic material that the mixing magnetic of different formulations is made and magnetic property see Table one and table two:
The density of the composite permanent-magnetic material that the mixing magnetic of table one different formulations is made
| The composition that mixes magnetic | Density p (g/cm after 500 ℃ of crystallization 3) |
| NdFeB | 6.227 |
| NdFeB: Fe base soft magnetism powder=9: 1 | 6.184 |
| NdFeB: Fe base soft magnetism powder=8: 2 | 6.175 |
| NdFeB: Fe base soft magnetism powder=7: 3 | 6.127 |
| NdFeB: Fe base soft magnetism powder=6: 4 | 6.145 |
| NdFeB: Fe base soft magnetism powder=5: 5 | 6.124 |
| NdFeB: Fe base soft magnetism powder=4: 6 | 6.122 |
| NdFeB: Fe base soft magnetism powder=3: 7 | 6.093 |
| NdFeB: Fe base soft magnetism powder=2: 8 | 6.084 |
| NdFeB: Fe base soft magnetism powder=1: 9 | 6.078 |
| Fe base soft magnetism powder | 5.978 |
The magnetic property of the composite permanent-magnetic material that the mixing magnetic of table two different formulations is made
| The composition that mixes magnetic | Br(kGs) | Hcb(koe) | Hcj(koe) | (BH)m(MGoe) |
| NdFeB | 7.125 | 5.769 | 8.861 | 10.67 |
| NdFeB: Fe base soft magnetism powder=9: 1 | 6.614 | 4.965 | 8.824 | 8.291 |
| NdFeB: Fe base soft magnetism powder=8: 2 | 6.192 | 4.173 | 8.497 | 6.407 |
| NdFeB: Fe base soft magnetism powder=7: 3 | 5.67 | 3.481 | 8.107 | 4.899 |
| NdFeB: Fe base soft magnetism powder=6: 4 | 5.278 | 2.865 | 7.34 | 3.643 |
| NdFeB: Fe base soft magnetism powder=5: 5 | 4.827 | 2.250 | 6.222 | 2.638 |
| NdFeB: Fe base soft magnetism powder=4: 6 | 4.454 | 1.646 | 3.657 | 1.758 |
| NdFeB: Fe base soft magnetism powder=3: 7 | 3.764 | 1.231 | 2.212 | 1.13 |
| NdFeB: Fe base soft magnetism powder=2: 8 | 3.124 | 0.7542 | 1.081 | 0.6281 |
| NdFeB: Fe base soft magnetism powder=1: 9 | 2.221 | 0.4273 | 0.5405 | 0.2512 |
| Fe base soft magnetism powder | 1.277 | 0.1885 | 0.2011 | 0.1256 |
Embodiment 2:
In the present embodiment, the prescription that mixes magnetic is NdFeB magnetic powder 80% (percetage by weight), iron-based soft magnetic powder 20% (percetage by weight); NdFeB magnetic powder is selected the MQP-B magnetic for use, preparation iron-based soft magnetic powder is selected iron silicon boryl alloy for use, be smelted into and carry out fast quenching behind the ingot casting and obtain amorphous thin ribbon, the crystallization temperature of amorphous thin ribbon is 500 ℃, crystallization time is 1 hour, after the crystallization in being filled with the vacuum sphere grinding machine of argon gas the time of ball milling be 20 minutes; Binding agent is selected epoxy resin for use, and content is 2% (percetage by weight), and the content that mixes magnetic is 98% (percetage by weight); Mix magnetic and coat processing, add binding agent then and mix with silane, compression moulding on press, briquetting pressure is elected 8T as, and formed body is φ 10 * 10mm.The density of composite permanent-magnetic material is 6.272g/cm
3, magnetic property is remanent magnetism Br=6.481KGs, magnetic strength coercivity H b=4.474koe, HCJ Hcj=8.937koe, maximum magnetic energy product (BH) m=7.16MGoe.
Embodiment 3:
In the present embodiment, the prescription that mixes magnetic is NdFeB magnetic powder 60% (percetage by weight), iron-based soft magnetic powder 40% (percetage by weight); NdFeB magnetic powder is selected the MQP-B magnetic for use, preparation iron-based soft magnetic powder is selected iron silicon boryl alloy for use, be smelted into and carry out fast quenching behind the ingot casting and obtain amorphous thin ribbon, the crystallization temperature of amorphous thin ribbon is 450 ℃, crystallization time is 1.5 hours, after the crystallization in being filled with the vacuum sphere grinding machine of argon gas the time of ball milling be 20 minutes; Binding agent is selected phenolic resins for use, and content is 3.5% (percetage by weight), and the content that mixes magnetic is 96.5% (percetage by weight); Mix magnetic and coat processing, add binding agent then and mix with silane, compression moulding on press, briquetting pressure is elected 10T as, and formed body is φ 10 * 10mm.The density of composite permanent-magnetic material is 5.941g/cm
3, magnetic property is remanent magnetism Br=5.122KGs, magnetic strength coercivity H b=2.865koe, HCJ Hcj=7.931koe, maximum magnetic energy product (BH) m=3.517MGoe.
Embodiment 4:
In the present embodiment, the prescription that mixes magnetic is NdFeB magnetic powder 20% (percetage by weight), iron-based soft magnetic powder 80% (percetage by weight); NdFeB magnetic powder is selected the MQP-B magnetic for use, preparation iron-based soft magnetic powder is selected iron silicon boryl alloy for use, be smelted into and carry out fast quenching behind the ingot casting and obtain amorphous thin ribbon, the crystallization temperature of amorphous thin ribbon is 400 ℃, crystallization time is 2 hours, after the crystallization in being filled with the vacuum sphere grinding machine of argon gas the time of ball milling be 25 minutes; Binding agent is selected epoxy resin for use, and content is 4.5% (percetage by weight), and the content that mixes magnetic is 95.5% (percetage by weight); Mix magnetic and coat processing, add binding agent then and mix with silane, compression moulding on press, briquetting pressure is elected 10T as, and formed body is φ 10 * 10mm.The density of composite permanent-magnetic material is 5.685g/cm
3, magnetic property is remanent magnetism Br=2.571KGs, magnetic strength coercivity H b=0.704koe, HCJ Hcj=1.068koe, maximum magnetic energy product (BH) m=0.5025MGoe.
Claims (5)
1, a kind of bonding type Nd-Fe-B, iron base soft magnetic powder bluk recombination permanent magnetic material is characterized in that this composite permanent-magnetic material is made up of neodymium iron boron, iron-based soft magnetic powder mixing magnetic and high polymer binder,
Described iron-based soft magnetic powder is that fast quenching became amorphous thin ribbon after iron was smelted into ingot casting, then amorphous thin ribbon is carried out crystallization and handles, and the ball milling in being filled with the vacuum sphere grinding machine of argon gas of the powder after the crystallization is prepared from.
2, bonding type Nd-Fe-B according to claim 1, iron base soft magnetic powder bluk recombination permanent magnetic material, the prescription that it is characterized in that mixing magnetic and high polymer binder percentage is by weight counted: mix magnetic 95%～98.5%, high polymer binder 1.5%～5%.
3, bonding type Nd-Fe-B according to claim 1 and 2, iron base soft magnetic powder bluk recombination permanent magnetic material, the prescription that it is characterized in that neodymium iron boron, iron-based soft magnetic powder mixing magnetic percentage is by weight counted: NdFeB magnetic powder 10%～90%, iron-based soft magnetic powder 10%～90%.
4, bonding type Nd-Fe-B according to claim 1 and 2, iron base soft magnetic powder bluk recombination permanent magnetic material is characterized in that this composite permanent-magnetic material surface coverage has the macromolecule resin coating.
5, bonding type Nd-Fe-B according to claim 3, iron base soft magnetic powder bluk recombination permanent magnetic material is characterized in that this composite permanent-magnetic material surface coverage has the macromolecule resin coating.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103440955A (en) * | 2013-09-10 | 2013-12-11 | 徐霞 | Compound agglutinated rear earth permanent magnet and preparation method thereof |
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