CN101615475A - A kind of manufacture method of flexible anisotropic bonding rare earth permanent magnet - Google Patents
A kind of manufacture method of flexible anisotropic bonding rare earth permanent magnet Download PDFInfo
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Abstract
A kind of manufacture method of flexible anisotropic bonding rare earth permanent magnet belongs to different in nature magnetic material preparation field.The present invention evenly mixes anisotropic magnet powder with suitable liquid macroimolecule material, under the action of a magnetic field, is prepared into magnetic and high molecular composite magnetic sheet, and wherein the direction of alignment magnetic field is parallel to the plane normal direction of composite magnetic sheet; After composite magnetic sheet solidified, the direction of easy axis of magnetic powder particles wherein just had been fixed on the plane normal direction of composite magnetic sheet; Composite magnetic sheet after solidifying is broken into powder, powder in the form of sheets, its direction of easy axis is parallel to the normal direction of sheet; With the composite magnetic powder and the rubber mix of this sheet, mixing after, when calendering formation, just can realize mechanical orientation; If when calendering formation, further apply magnetic field orientating, just can realize mechanical orientation and magnetic field orientating simultaneously, have the more flexible anisotropic bonding magnet of high-orientation thereby prepare.
Description
Technical field
The invention belongs to different in nature magnetic material preparation field, be specifically related to a kind of preparation method of flexible anisotropic bonding rare earth permanent magnet.
Background technology
Flexible magnet is the elastic magnetic material that is formed by magnetic, rubber and the meticulous manufacturing of a spot of compounding ingredient process, is characterized in good flexibility and magnetic property, and is non-friable, is convenient to transportation, assembling, easy to use; Size can be by cutting any adjustment, and the shape of product variation can be made into goods of ultra-thin, overlength, super wide continuous sheet, band and different shape etc.; Need not mould, sample is quick; Production procedure is short, the efficient height, and processing cost is low; Rim charge can reclaim fully, and energy consumption is low etc.
The annual consumption of whole world bendable permanent magnet body reaches 1.7 ten thousand tons according to incompletely statistics, and what wherein the overwhelming majority was used all is the pliability ferrite permanent magnet.But along with application constantly proposes ultra-thin, ultralight, stable, powerful requirement to components and parts, audio-visual equipment space required such as music hall, square, family is bigger, thickness is thinner, the high-fidelity planar loudspeaker that power is higher, need thinner in the laptop computer, more powerful fan motor is to satisfy the heat radiation requirement of high speed processing chip, also need the direct driving motor of more steady, bigger moment etc. in the household electrical appliances such as washing machine, fan, the pliability ferrite is because the low (maximum magnetic energy product≤18kJ/m of magnetic
3), can not satisfy instructions for use.
In permanent magnetic material, with Nd
2Fe
14B is that the NdFeB and the SmCo permanent magnet of matrix has more excellent magnetism energy.Therefore, preparation has more that the sight of the pliability magnet of high magnetic characteristics has focused on this class material.And mainly be the isotropic flexible calendering magnet of preparation to the research of this type of material, according to some patent reports both at home and abroad, at present for the flexible isotropic magnet of isotropism NdFeB magnetic powders, its magnetic energy product≤68KJ/m
3
In recent years, along with the active demand of further slimming of information products and high efficiency, the performance of magnetic material is had higher requirement again, people attempt to seek the pliability magnet with higher permanent magnetism performance.Have more the anisotropic magnet powder of high magnetic characteristics than isotropism magnetic and prepare the flexible anisotropic magnet and just become the preferred plan that addresses this problem and utilize.At present for aspect the preparation of flexible anisotropic magnet, general magnetic all adopts anisotropic ferrite powder, mainly be to utilize this class powder to have the characteristics oriented moulding of shape anisotropy, even adopt the method for external magnetic field orientation, required alignment magnetic field generally is no more than 800kA/m, and its maximum magnetic energy product is no more than 18kJ/m
3And have than ferrite magnetic such as the anisotropy NdFeB of high magnetic characteristics or SmCo more, owing to do not have shape anisotropy, and coercive force very high again (generally greater than 960kA/m), present alignment magnetic field (generally requiring the coercive force of alignment magnetic field greater than twice) are difficult to the orientation effect that reaches good.
In the CN200410052150.3 patent documentation, introduced the preparation method of flexible isotropism neodymium iron boron magnetic body, promptly mix in proportion by the rubber-like binding agent of handling through modification and neodymium iron boron class magnetic and processing aid, mixed method adopts the banburying method, opens refining method, paddling process or screw mixing method, sizing material after will mixing then adopts rolling process or dull and stereotyped pressing to make certain thickness magnet, and wherein the weight content of each component is: neodymium iron boron class magnetic 87～97%, modified rubber class binding agent 1～8%, processing aid 0～5%.With this kind method generally all is the isotropism flexible adhesion magnet of preparing.
In the CN200610089368.5 patent documentation, magnetic aligning anisotropy calendering bonded permanent magnet and preparation method thereof and magnetic calender have been introduced, promptly this method comprises the process of material being carried out granulation and moulding, material comprises magnetic, binding agent, coupling agent and compounding ingredient, wherein moulding comprises that the material after the granulation is carried out magnetic aligning on the magnetic calender rolling, and at least one roller of this magnetic calender is that hollow structure and in-built electrical magnet are to produce alignment magnetic field.The main innovate point of this method is exactly to add electromagnet in the roller to traditional calender, thereby produces alignment magnetic field, and material will be orientated under the action of a magnetic field in by roller like this, thus the generation anisotropy magnet.The ferrite powder that it is raw material that but this method is applicable to cheap iron phosphorus prepares calendering formation magnetic aligning bonded permanent magnet.The coercive force of ferrite powder is lower, therefore the requirement of strength of alignment magnetic field is not high, so this class electromagnetic field ratio is easier to realize, but for the NdFeB magnetic, just be difficult to realize, the coercive force of NdFeB magnetic is very high, the desired alignment magnetic field that adds is very high, and the electromagnetic field that adds of this hard intensity is to be difficult to realize for rolling equipment.Simultaneously, this method that adds magnetic field in the calender roller, orientation effect are not very desirable.Therefore make separately and be not suitable for preparation anisotropy flexible adhesion NdFeB magnet in this way.
In the CN200610113210.7 patent documentation, introducing with specific rapid hardening slice technique manufacturing is the alloy of base with neodymium (or praseodymium) iron, make magnetic RxFe100-x-y-zMyIz by pulverizing behind the gas-solid phase reaction then, this magnetic is the platy-monocrystal particle of particle mean size 1-3 μ m.Utilize the prepared magnetic of this technology, not only have the magnetocrystalline anisotropy of orientation under the outside magnetic field effect, and have rolling anisotropic and stress anisotropy.The invention provides the method for preparing high-performance anisotropy calendering flexible rubber magnet according to these three kinds of anisotropy.Employed magnetic is rare-earth-iron-nitrogen series permanent magnetic material in this invention, and this material shape anisotropy and magnetocrystalline anisotropy will occur and deposits when being crushed to 1-3 μ m, so this magnetic can directly be used for preparing the flexible anisotropic magnet.This is a character itself that utilize this class magnetic just to have shape anisotropy and magnetocrystalline anisotropy and deposit.And the character that the rare-earth-iron-boron based material does not just possess this shape anisotropy and magnetocrystalline anisotropy and deposits only has magnetocrystalline anisotropy, so can not directly prepare anisotropy magnet by the method for rolling.
In the CN200610113209.4 patent documentation, introduced a kind of anisotropic rare earth permanent-magnetic material that has, have Th
[2]Zn
[17]Type crystal structure is (Sm with the represented composition of atomic percent
[1-a]R
[a])
[x]Fe
[100-x-y-z]M
[y]I
[z], in the formula: R is the combination of Pr or Pr and other rare earth element, 0.01≤α≤0.30; M is selected from Si, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Nb, Mo, Al and Zr; I is the combination of independent N or N and C; 7≤x≤12,0.01≤y≤8.0,6≤z≤14.4.Utilize specific technology to make particle mean size and be 1-3 μ m single crystal grain magnetic in the form of sheets, this magnetic not only has the magnetocrystalline anisotropy of orientation under the outside magnetic field effect, and have rolling anisotropic and a stress anisotropy, provide the method for preparing high-performance anisotropy calendering flexible rubber magnet according to these three kinds of anisotropy, what this invention and CN200610113210.7 were introduced is actually with a kind of method.All be that to utilize rare-earth-iron-nitrogen be magnetic has shape anisotropy and magnetocrystalline anisotropy and deposits when 1-3 μ m character, and rare-earth-iron-boron to be magnetic just do not possess this character.So rare-earth-iron-boron is a magnetic directly adopt calendering technology be can not obtain anisotropic, must make rare-earth-iron-boron by other method is that magnetic has shape anisotropy and magnetocrystalline anisotropy simultaneously, could prepare anisotropy magnet by calendering technology like this.
Summary of the invention
It is compound with anisotropy NdFeB magnetic powder (100 orders are following) and macromolecular material physics by preliminary treatment to the objective of the invention is to elder generation, is prepared into film under the action of a magnetic field, then with the film fragmentation, obtains the sheet composite magnetic powder.During calendering formation, the sheet composite magnetic powder is realized mechanical orientation, prepares the flexible anisotropic magnet, thereby improves the magnet magnetic property.
Preparation process of the present invention is as follows:
1, anisotropic magnet powder is evenly mixed with the liquid macroimolecule material, the proportioning of magnetic and macromolecular material is by mass percentage: anisotropic magnet powder 70%-90%, macromolecular material 30%-10%, apply more than the 4000Oe of magnetic field, under the action of a magnetic field, obtain magnetic and high molecular composite magnetic sheet, wherein the direction of alignment magnetic field is parallel to the plane normal direction of composite magnetic sheet; After composite magnetic sheet solidified, the direction of easy axis of magnetic powder particles wherein was fixed on the plane normal direction of composite magnetic sheet; Composite magnetic sheet after solidifying is broken into powder, obtains composite magnetic powder, powder in the form of sheets, its direction of easy axis is parallel to the normal direction of sheet.
2, the composite magnetic powder with this sheet mixes with rubber, processing aid etc., mixing after, calendering formation is realized mechanical orientation; Or when calendering formation, further apply more than the 10000Oe of magnetic field, realize mechanical orientation and magnetic field orientating simultaneously, obtain the flexible anisotropic magnet.
Composite magnetic powder and rubber, the ratio between the processing aid are composite magnetic powder 80%-98% by mass percentage, and rubber is 1.5%-20%, and processing aid is 0.5%-10%.
The particle diameter of anisotropy NdFeB magnetic powder is unlikely to excessive with the particle that guarantees composite magnetic powder, and causes rough, the out-of-flatness of magnet surface below 150 microns.
The particle diameter of the composite magnetic powder of described sheet is below 250 microns.
Used magnetic adopts the HDDR anisotropy NdFeB magnetic with magnetocrystalline anisotropy, also can adopt magnetics such as SmCo, SmFeN.
It is to be the macromolecular material of characteristics such as rigidity and fragility are big, high temperature resistant after liquid state, low-temperature setting, the curing that used macromolecular material adopts epoxy resin or modification acrylate etc. to have normal temperature.
Compared with prior art, the characteristics of maximum of the present invention are: will only have the magnetic of magnetocrystalline anisotropy, after the pretreated method processing by the present invention's introduction, magnetic just has shape anisotropy and magnetocrystalline anisotropy simultaneously, and its direction of easy axis is parallel with the short-axis direction of sheet magnetic.Sheet composite magnetic powder is in calender line, during pressure roller by calender, the composite magnetic powder particle of sheet is rotated in basis material, the platen surface of its sheet is regularly arranged perpendicular to external force direction, on the roll pressure direction, form gathering of easy magnetizing axis, form composite magnetic powder particle orientation, thereby produce the anisotropy flexible magnet, realize mechanical orientation, its direction of easy axis is parallel with the plane normal direction of flexible magnet.Magnetic after handling like this just can directly be prepared anisotropy magnet by calendering technology.This provides strong basis for the range of application that enlarges flexible magnet significantly.If not by preliminary treatment, directly anisotropic magnet powder is passed through calendering technology, what prepare is isotropic magnet, even add magnetic field on the roller of calender, orientation effect is also very poor, surpasses 20000Oe electromagnetism orientation apparatus because present rolling equipment is difficult to be equipped with magnetic field.And this preliminary treatment of the present invention generates shape anisotropy for the Magnaglo that does not have shape anisotropy.In the process of calendering, just make the rare earth permanent-magnet powder that does not have shape anisotropy originally, can not magnetic field orientating can realize the associating of mechanical orientation or mechanical orientation and magnetic field orientating subsequently, thereby improved its orientation effect effectively, improved its magnetic property widely.
Embodiment
Be specifically described by the following examples.
Implementation column 1
The magnet prescription is: the percentage by weight of various components is respectively: HDDR anisotropy NdFeB magnetic 85% in the composite magnetic powder, modification acrylate class 15% under magnetic field (4000Oe) effect, obtains magnetic and high molecular composite magnetic sheet.Composite magnetic sheet after solidifying is broken into powder, obtains the sheet composite magnetic powder, its direction of easy axis is parallel to the normal direction of sheet.With composite magnetic powder in the magnet 90%, haloflex 8.8%, silane coupler 0.2%, phthalate plasticizers 0.3%, stearate lubricant 0.2%, components such as ketoamine class antioxidant 0.5% adopt mixing roll mixing to evenly, mixture are made the magnetic sheet that thickness is 2mm in calender again.Gained magnet maximum magnetic energy product is 10.5MGOe.
Implementation column 2
The magnet prescription is: the percentage by weight of various components is respectively: HDDR anisotropy NdFeB magnetic 85% in the composite magnetic powder, epoxylite 15% under magnetic field (4000Oe) effect, obtains magnetic and high molecular composite magnetic sheet.Composite magnetic sheet after solidifying is broken into powder, obtains the sheet composite magnetic powder, its direction of easy axis is parallel to the normal direction of sheet.Then with anisotropy composite magnetic powder 90% in the magnet, haloflex 8.8%, silane coupler 0.2%, phthalate plasticizers 0.3%, stearate lubricant 0.2%, components such as ketoamine class antioxidant 0.5% adopt mixing roll mixing to evenly, mixture are made the magnetic sheet that thickness is 2mm in calender again.Gained magnet maximum magnetic energy product is for being 11.1MGOe.
Implementation column 3
The magnet prescription is: the percentage by weight of various components is respectively: HDDR anisotropy NdFeB magnetic 90% in the composite magnetic powder, epoxylite 10% under magnetic field (4000Oe) effect, obtains magnetic and high molecular composite magnetic sheet.Composite magnetic sheet after solidifying is broken into powder, obtains the sheet composite magnetic powder, its direction of easy axis is parallel to the normal direction of sheet.Then with composite magnetic powder in the magnet 90%, haloflex 8.8%, silane coupler 0.2%, phthalate plasticizers 0.3%, stearate lubricant 0.2%, components such as ketoamine class antioxidant 0.5% adopt mixing roll mixing to evenly, and mixture is made the magnetic sheet that thickness is 2mm in calender.Gained magnet maximum magnetic energy product is 12.3MGOe.
Implementation column 4
The magnet prescription is: the percentage by weight of various components is respectively: HDDR anisotropy NdFeB magnetic 90% in the composite magnetic powder, epoxylite 10% under magnetic field (4000Oe) effect, obtains magnetic and high molecular composite magnetic sheet.Composite magnetic sheet after solidifying is broken into powder, obtains the sheet composite magnetic powder, its direction of easy axis is parallel to the normal direction of sheet.Then with composite magnetic powder in the magnet 90%, haloflex 8.8%, silane coupler 0.2%, phthalate plasticizers 0.3%, stearate lubricant 0.2%, above component such as ketoamine class antioxidant 0.5% adopts mixing roll mixing to evenly, again mixture is made the magnetic sheet that thickness is 2mm in the calender that has externally-applied magnetic field (10000Oe magnetic field orientating).Gained magnet maximum magnetic energy product is 9.5MGOe.
Implementation column 5
The magnet prescription is: the percentage by weight of various components is respectively: HDDR anisotropy NdFeB magnetic 90% in the composite magnetic powder, epoxylite 10% under magnetic field (4000Oe) effect, obtains magnetic and high molecular composite magnetic sheet.Composite magnetic sheet after solidifying is broken into powder, obtains the sheet composite magnetic powder, its direction of easy axis is parallel to the normal direction of sheet.Then with composite magnetic powder in the magnet 90%, haloflex 8.8%, silane coupler 0.2%, phthalate plasticizers 0.3%, stearate lubricant 0.2%, above component such as ketoamine class antioxidant 0.5% adopt mixing roll mixing to even, mixture is made thickness be magnetic sheet in calender (mechanical orientation) greater than 2mm, then with magnetic sheet by having the calender of externally-applied magnetic field (10000Oe magnetic field orientating), at a certain temperature, roll into the magnetic sheet of 2mm.Gained magnet maximum magnetic energy product is 14.0MGOe.
Claims (6)
1, a kind of manufacture method of flexible anisotropic bonding rare earth permanent magnet, it is characterized in that, anisotropic magnet powder is evenly mixed with the liquid macroimolecule material, the proportioning of magnetic and macromolecular material is by mass percentage: anisotropic magnet powder 70%-90%, macromolecular material 30%-10%, apply more than the 4000Oe of magnetic field, obtain magnetic and high molecular composite magnetic sheet, wherein the direction of alignment magnetic field is parallel to the plane normal direction of composite magnetic sheet; After composite magnetic sheet solidified, the direction of easy axis of magnetic powder particles wherein was fixed on the plane normal direction of composite magnetic sheet; Composite magnetic sheet after solidifying is broken into powder, obtains composite magnetic powder, powder in the form of sheets, its direction of easy axis is parallel to the normal direction of sheet; The composite magnetic powder of this sheet is mixed with rubber, processing aid, mixing after, calendering formation is realized mechanical orientation; Or when calendering formation, further apply more than the 10000Oe of magnetic field, realize mechanical orientation and magnetic field orientating simultaneously, obtain the flexible anisotropic magnet.
2, manufacture method as claimed in claim 1 is characterized in that, composite magnetic powder and rubber, and the ratio between the processing aid is composite magnetic powder 80%-98% by mass percentage, and rubber is 1.5%-20%, and processing aid is 0.5%-10%.
3, manufacture method as claimed in claim 1 is characterized in that, the particle diameter of anisotropy NdFeB magnetic powder is below 150 microns.
4, manufacture method as claimed in claim 1 is characterized in that, the particle diameter of the composite magnetic powder of described sheet is below 250 microns.
5, manufacture method as claimed in claim 1 is characterized in that, used magnetic adopts HDDR anisotropy NdFeB magnetic or SmCo magnetic or the SmFeN magnetic with magnetocrystalline anisotropy.
6, manufacture method as claimed in claim 1 is characterized in that, used macromolecular material is epoxy resin or modification acrylate.
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| CN102050259A (en) * | 2010-12-05 | 2011-05-11 | 蔡忠贞 | Method for preventing counterfeit and burglary by using plastic film |
| CN102360653A (en) * | 2011-06-08 | 2012-02-22 | 北矿磁材科技股份有限公司 | Flexible rare earth bonded magnet with roll anisotropy and manufacturing method thereof |
| CN102779603A (en) * | 2012-07-03 | 2012-11-14 | 大地熊（苏州）磁铁有限公司 | Flexible bonding neodymium iron boron magnet and preparation process thereof |
| CN103745798A (en) * | 2014-01-09 | 2014-04-23 | 浙江和也健康科技有限公司 | Rare earth flexible magnetic stripe for health bedding and preparation method thereof |
| CN105225780A (en) * | 2015-10-12 | 2016-01-06 | 北京工业大学 | A kind of high temperature resistant anisotropic bond samarium iron nitrogen magnet and preparation method thereof |
| CN105623240A (en) * | 2015-12-17 | 2016-06-01 | 上海交通大学 | Anisotropic high-molecular permanent magnetic compound material and preparation method therefor |
| CN114023551A (en) * | 2021-10-12 | 2022-02-08 | 横店集团东磁股份有限公司 | Anisotropic rubber composite rare earth permanent magnet orientation forming process |
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| CN115020099A (en) * | 2022-05-26 | 2022-09-06 | 中国科学院金属研究所 | Method for enhancing vertical magnetic anisotropy of NdFeB-based permanent magnet thick film |
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| CN1594209A (en) * | 2004-06-28 | 2005-03-16 | 广州金南磁塑有限公司 | Flexible rare-earth bonded magnet and its manufacturing method |
| CN100437841C (en) * | 2006-09-19 | 2008-11-26 | 北京大学 | Anisotropic rare-earth permanent magnet material and its magnetic powder and magnet mfg. method |
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| CN102360653B (en) * | 2011-06-08 | 2014-08-27 | 北矿磁材科技股份有限公司 | Flexible rare earth bonded magnet with roll anisotropy and manufacturing method thereof |
| CN102360653A (en) * | 2011-06-08 | 2012-02-22 | 北矿磁材科技股份有限公司 | Flexible rare earth bonded magnet with roll anisotropy and manufacturing method thereof |
| CN102779603A (en) * | 2012-07-03 | 2012-11-14 | 大地熊（苏州）磁铁有限公司 | Flexible bonding neodymium iron boron magnet and preparation process thereof |
| CN103745798B (en) * | 2014-01-09 | 2016-01-20 | 浙江和也健康科技有限公司 | A kind of health-care bedding rare-earth flexible magnetic stripe and preparation method thereof |
| CN103745798A (en) * | 2014-01-09 | 2014-04-23 | 浙江和也健康科技有限公司 | Rare earth flexible magnetic stripe for health bedding and preparation method thereof |
| CN105225780A (en) * | 2015-10-12 | 2016-01-06 | 北京工业大学 | A kind of high temperature resistant anisotropic bond samarium iron nitrogen magnet and preparation method thereof |
| CN105225780B (en) * | 2015-10-12 | 2017-11-14 | 北京工业大学 | A kind of high temperature resistant anisotropic bond samarium iron nitrogen magnet and preparation method thereof |
| CN105623240A (en) * | 2015-12-17 | 2016-06-01 | 上海交通大学 | Anisotropic high-molecular permanent magnetic compound material and preparation method therefor |
| CN114023551A (en) * | 2021-10-12 | 2022-02-08 | 横店集团东磁股份有限公司 | Anisotropic rubber composite rare earth permanent magnet orientation forming process |
| CN114023551B (en) * | 2021-10-12 | 2023-03-14 | 横店集团东磁股份有限公司 | Anisotropic rubber composite rare earth permanent magnet orientation forming process |
| CN114597638A (en) * | 2022-03-09 | 2022-06-07 | 清华大学 | Flexible magnetoelectric composite low-frequency mechanical antenna and preparation method thereof |
| CN115020099A (en) * | 2022-05-26 | 2022-09-06 | 中国科学院金属研究所 | Method for enhancing vertical magnetic anisotropy of NdFeB-based permanent magnet thick film |
| CN115020099B (en) * | 2022-05-26 | 2023-11-03 | 中国科学院金属研究所 | Method for enhancing vertical magnetic anisotropy of NdFeB-based permanent magnet thick film |
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