CN104032263B - A kind of method of vacuum vapor plating and a kind of rare-earth magnet covering evaporation coating - Google Patents
A kind of method of vacuum vapor plating and a kind of rare-earth magnet covering evaporation coating Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 61
- 239000011248 coating agent Substances 0.000 title claims abstract description 59
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 59
- 238000001704 evaporation Methods 0.000 title claims abstract description 46
- 230000008020 evaporation Effects 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000007747 plating Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000007769 metal material Substances 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 238000009834 vaporization Methods 0.000 claims abstract description 17
- 230000008016 vaporization Effects 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000002203 pretreatment Methods 0.000 claims abstract description 3
- 238000009826 distribution Methods 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005649 metathesis reaction Methods 0.000 abstract description 4
- 239000011777 magnesium Substances 0.000 description 31
- 239000010408 film Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000004453 electron probe microanalysis Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000005488 sandblasting Methods 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 238000013467 fragmentation Methods 0.000 description 4
- 238000006062 fragmentation reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010409 ironing Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 230000005012 migration Effects 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 238000007598 dipping method Methods 0.000 description 1
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- 238000009713 electroplating Methods 0.000 description 1
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- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
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- Manufacturing Cores, Coils, And Magnets (AREA)
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Abstract
The invention discloses a kind of method of vacuum vapor plating and a kind of rare-earth magnet covering evaporation coating, the method comprises following step: after 1) rare-earth magnet workpiece carries out pre-treatment, be contained on work rest; 2) described work rest is sent into reaction chamber, preoxidation; 3) described work rest is sent into coating chamber, vacuumize, evaporation of metal material M is heated to vaporization temperature, evaporation is carried out to described rare-earth magnet workpiece; 4) lower the temperature, vacuum breaker, takes out workpiece and obtains.The method is by carrying out micro-oxidation to rare-earth magnet in advance, then passing into the over oxidation that the mode of M steam generation replacement(metathesis)reaction prevents rare-earth magnet, and obtains fine and close MO and to distribute thin layer and distributing the M layer that thin layer is firmly connected with this MO.
Description
Technical field
The present invention relates to the manufacturing technology field of magnet, particularly relate to a kind of method of vacuum vapor plating and a kind of rare-earth magnet covering evaporation coating.
Background technology
Because rare-earth magnet gets rusty easily, therefore, need aborning to carry out coating conservation treatment to its surface.And there is very large limitation in traditional electrochemical plating, it is not only difficult to control thickness of coating, and coating surface easily produces pit, firmly stings, peels, burns, the defect such as spot, shadow, buildup, this will shorten the work-ing life of ndfeb magnet, the waste water simultaneously electroplating generation needs secondary treatment qualified discharge, both production cost was improved, unfavorable to environment again.
Utilize vacuum evaporation coating membrane technique can avoid above-mentioned many disadvantages, and Principle of plating is simple, processing ease, film forming speed are fast, efficiency is high, economical and practical, not pollution.For rare-earth magnet, conventional plated film is the metallic membrane of Mg, Al or Zn etc. or the alloy film of above-mentioned metallic combination or SiO
2films etc., this is wherein common with the metallic membrane of Mg or Al.But for the rare-earth magnet metal coating that existing mode is obtained, Mg, Al, Zn plated film and the ironing surface bonding force of Rare-Earth Magnetic are far below MgO, Al
2o
3, ZnO and the ironing surface bonding force of Rare-Earth Magnetic, easily peel off from magnet surface, protected effect is not good.
At present, serve as protective dielectric layer with MgO vacuum vapor plating and on glass and silicon chip, be able to a large amount of use, when carrying out MgO plated film; general use MgO is as target; with electron beam or laser focusing MgO target surface, MgO is made to melt and be evaporated, but this mode high cost.For addressing this problem; patent of invention CN1156600C adopts S-gun-type magnetic control sputtering method; to make target in cone shape pure magnesium; Ar gas is shielding gas, and oxygen is reactant gases, obtains thickness and is about 0.5 ~ 1.2 μm, the MgO function film of dense uniform; but this plated film mode uses oxygen in a large number; for rare-earth magnet, easily cause over oxidation, have a strong impact on product performance, use when not therefore being adapted at rare-earth magnet plated film.
Summary of the invention
An object of the present invention is the deficiency overcoming prior art, a kind of method of vacuum vapor plating is provided, it is by carrying out micro-oxidation to rare-earth magnet in advance, then passing into the MO distribution layer that the mode of M steam generation replacement(metathesis)reaction obtains densification and the M layer be firmly connected with this MO distribution layer, thus prevents the over oxidation of rare-earth magnet.
The technical solution adopted for the present invention to solve the technical problems is:
A method for rare-earth magnet vacuum vapor plating, rare-earth magnet of the present invention is for containing R
2t
14the magnet of B principal phase, described R is selected from least one comprised in the rare earth element of yttrium, and described T is at least one transition metal comprising Fe, it is characterized in that, comprises the following steps:
1), after rare-earth magnet workpiece carries out pre-treatment, be contained on work rest;
2) described work rest is sent into reaction chamber, preoxidation;
3) described work rest is sent into coating chamber, be evacuated to gauge pressure 10
-1~ 10
-6after Pa, evaporation of metal material M is heated to vaporization temperature, evaporation is carried out to described rare-earth magnet workpiece;
4) lower the temperature, vacuum breaker, takes out workpiece and obtains.
After above-mentioned steps process, the surface of rare-earth magnet defines MO distribution layer, and the M film coating formed on described MO distribution layer, and wherein, the formation basic theory of MO distribution layer is as follows:
As the R of rare-earth magnet principal phase
2fe
14b, R are oxidized under aerobic state: 2R
2fe
14b+3O
2→ 2R
2o
3+ 2B+28Fe, the Gibbs free energy Δ G<0 of this reaction, forward is spontaneous to carry out; Also there is following reaction in rich R phase simultaneously: 4R+3O
2→ 2R
2o
3.
Afterwards, R
2o
3react with Fe, generate Fe
2o
3deng product.
Afterwards, in step 3) vacuum environment under, there is provided enough heat to obtain the vapour pressure needed for evaporation to thing M to be evaporated, at a proper temperature, evaporation particle condenses on substrate, so just can realize vacuum-evaporation thin film deposition, after evaporation of metal material M is attached to metallic surface, because it has stronger betatopic ability as reductive agent, electron transfer processes occurs at interface, electronics transfers to Fe from M atom
2o
3in Fe atomic surface, Fe is restored, form the positive ion of M simultaneously, now, attracting each other between the change of the chemical potential gradient caused due to electronic migration and charged ion, and in lattice, produce room because Fe ion is reduced, cause the mutual diffusion in ionic crystal, make M ion and O ion utilize in interface vacancy mechanism spread mutually and combine, form chemical bond and connect, obtain distribution range and the Fe of MO
2o
3the distribution of zone of oxidation is quite or slightly larger than Fe
2o
3distribution (metal is by diffusing in rare-earth magnet).Along with the prolongation of time, such process is constantly carried out, and finally makes M and metal interface reach chemistry comparatively completely and is connected, can be attached to magnet surface securely.
After above-mentioned process, rare-earth magnet is no longer directly combined with metal plating, but interval MO distribution layer is combined with metal plating, thus improves the bonding force between metal plating and rare-earth magnet, play its provide protection.
Can infer from above-mentioned explanation, in the present invention, the process of the process and plated film that form MO layer is carried out simultaneously.
The bonding force testing method that the present invention adopts is as follows: adopt cutting edge angle 30 °, and the single-point tool that cutting edge thickness is 50 ~ 100 μm cuts in the length and width direction that is parallel in the same length and width face of magnetic sheet each 11 of the line of cut that spacing is 2mm.During cutting, cutter wants consistent with the angle of magnetic sheet, and firmly evenly, cutting edge will just in time can penetrate coating and touch substrate in cutting.Check result classification is in table 1.
Table 1 check result hierarchical table
It should be added that, the pretreatment procedure that the present invention mentions can be at least one being selected from sandblasting, purge or pickling etc.
In the embodiment recommended, step 2) in, Pre oxidation is 100 ~ 600 DEG C, and preoxidation time is 0.1 ~ 12 hour.Generally speaking, Fe
2o
3spreading depth increase with the increase of oxidization time, within the above-mentioned treatment time, Fe
2o
3spreading depth be within magnet function surface 0.05 ~ 5 μm.
In above-mentioned process, need special rate-determining steps 2) oxidization time, if oxidization time is long, a large amount of Fe can be caused
2o
3formation, magnetic property decline, oxidization time is too short, and MO distribution layer can be caused excessively thin, and low with the bonding force of magnet surface, metallic diaphragm easily comes off.
In the embodiment recommended, step 3) in, the evaporation time is 0.05 ~ 3 hour.The time of evaporation time of the present invention needed for conventional evaporation, without the need to specially extending or shortening.
In the embodiment recommended, described rare-earth magnet is NdFeB based magnet.
Recommend embodiment in, also need strict rate-determining steps 2) relative humidity, in hygrothermal environment fine and close NdFeB sintered magnet main corrosion reaction be: Nd+3H
2o → Nd (OH)
3+ 3H, the hydrogen be reduced very easily is absorbed by rare earth intermetallic compound, and reacts further mutually with the rich neodymium of crystal boundary, and cause grain boundary corrosion, its reaction formula is as follows: Nd+3H → NdH
3, NdH
3the generation of phase causes rich neodymium phase volume to expand, and lattice is expanded, and embrittlement of grain boundaries is loosened, and main phase grain peels off.In the present invention, need by step 2) relative humidity control below 10%, to ensure magnet performance, and enable plated film be attached to magnet surface securely.
In the embodiment recommended, for preventing the transfer of material, the unlatching etc. of reaction chamber brings steam, therefore, step 2) described reaction chamber can directly be used as step 3) described coating chamber, and in described step 2) complete after, closedown oxygen.
In the embodiment recommended, in step 3) after, be also provided with following step, continue to pass into O
2, evaporation of metal material M is heated to vaporization temperature simultaneously, to described workpiece evaporation 0.05 ~ 1 hour, the outside surface of M layer forms MO layer.
In the embodiment recommended, in step 3) after, be also provided with following step, heat-treat the workpiece completing evaporation, thermal treatment temp is 80 ~ 300 DEG C, and heat treatment time is 0.5 ~ 12h.
In the embodiment recommended, described evaporating materials is Mg, and the Schwellenwert of described vaporization temperature is 650 DEG C.After Mg is attached to metallic surface, because it has stronger betatopic ability as reductive agent, electron transfer processes occurs at interface, electronics transfers to Fe from Mg atom
2o
3in Fe atomic surface, Fe is restored, forms the positive divalent ion of Mg simultaneously.Attracting each other between the change of the chemical potential gradient now caused due to electronic migration and charged ion, and in lattice, produce room because Fe ion is reduced, cause the mutual diffusion in ionic crystal, Mg ion and O ion is made to utilize vacancy mechanism spread mutually and combine in interface, formation chemical bond connects, MgO layer can improve the bonding force between Mg coating and rare-earth magnet matrix, isolate magnet and extraneous contact simultaneously, play provide protection, fine and close Mg layer has cut off the contact of magnet and air, because chemically reactive is high, first react in the presence of a harsh environment, thus play the effect of protection rare-earth magnet.
In the embodiment recommended, described evaporation of metal material is Al, and the Schwellenwert of described vaporization temperature is 980 DEG C.Effect is see Mg section.
In the embodiment recommended, described evaporation of metal material is Zn, and the Schwellenwert of described vaporization temperature is 500 DEG C.Effect is see Mg section.
In the embodiment recommended, described evaporation of metal material is Mg and Al, and the Schwellenwert of described vaporization temperature is 650 DEG C and 980 DEG C.Effect is see Mg section.
In the embodiment recommended, described evaporation of metal material is Mg and Zn, and the Schwellenwert of described vaporization temperature is respectively 650 DEG C and 500 DEG C.Effect is see Mg section.
In the above-described embodiment, there is following replacement(metathesis)reaction with the ferric oxide on surface in the metallic film be deposited on magnet:
Fe
2o
3+ 3 (Mg/Zn) → 2Fe+3 (Mg/Zn) O, or Fe
2o
3+ 2Al → 2Fe+Al
2o
3
Certainly, also can be other evaporation of metal material, its prerequisite be that this evaporation of metal material is stable under the use temperature of rare-earth magnet, and can with Fe
2o
3reaction oxidizing reaction, and the performance of rare-earth magnet can not be affected.
Recommend embodiment in, step 3) in also evaporator room is set, the temperature of described evaporator room exceedes the vaporization temperature of described evaporation of metal material, and the temperature of described coating chamber controls at 200 ~ 400 DEG C.Coating chamber is controlled after said temperature, velocity of diffusion and the Fe of M can be accelerated
2o
3with the speed of response of M, thus make Fe
2o
3in oxygen all react with material M to be evaporated, formed MO.
Another object of the present invention is to provide a kind of vacuum vapor plating of novel texture.
Cover a rare-earth magnet for evaporation coating, it is characterized in that: it is included in the MO distribution layer of rare-earth magnet surface formation and the M layer outside described MO distribution layer, and described M is selected from least one of Mg, Al or Zn.
It should be noted that, MO distribution layer is here generally successive layers, and this successive layers does not refer in particular to the horizontal layer of consistency of thickness, also can be the dipping bed that thickness increases gradually or reduces gradually, buckle layer that also can be in uneven thickness; Certainly, minority is under extremely special working condition, and MO distribution layer also may form zone of fracture.No matter the form of MO layer how, as long as under it meets and do not affect the prerequisite of magnet performance and the bonding force between M layer and magnet, the MO layer of above-mentioned form all should be put into protection scope of the present invention simultaneously.
Compared with prior art, the present invention has following feature:
1) the present invention is by carrying out micro-oxidation to rare-earth magnet in advance, then passing into the MO distribution layer that the mode of M steam generation replacement(metathesis)reaction obtains densification and the M layer be firmly connected with MO distribution layer, thus prevents the over oxidation of rare-earth magnet.
2) the method had both overcome M layer and the weak problem of rare-earth magnet bonding force, overcame again the oxidative damage problem to rare-earth magnet in existing MO layer plated film forming process.
3) the present invention carries out in low-humidity environment, thus the danger that can prevent principal phase from peeling off, enable plated film be attached to magnet surface securely.
4) the present invention takes full advantage of the feature of rare-earth magnet, and determines optimal preoxidation time and Pre oxidation, makes Fe
2o
3spreading depth be 0.05 ~ 5 μm of below magnet function surface, and then make the distribute spreading depth of thin layer of MO be 0.05 ~ 5 μm of below magnet function surface, thus ensure that cohesive strength, prevent coming off of metallic diaphragm, be unlikely to again to affect magnet performance.
5) the present invention can select to carry out in same indoor to be oxidized and the operation of plated film, and to prevent the transfer of material, the unlatching etc. of reaction chamber brings steam, affects coating effects.
Accompanying drawing explanation
Fig. 1 is Fe element, O element and Mg element at the concentration profile of coating and substrate.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment one
Prepare rare-earth magnet sintered compact, this sintered compact has following atom composition: Dy is 5, Lu be 0.2, Er be 0.2, Nd be 8.5, Tm is 0.5, Y is 0.1, Co be 1, C be 0.05, B be 7, Cu is 0.2, Mn is 0.2, Ga be 0.2, Bi be 0.1, Ti be 0.3, Fe is surplus.Obtain according to the melting of existing rare-earth magnet, rejection tablet, hydrogen fragmentation, airflow milling, compacting, sintering and heat treated operation.
Be processed into the magnet of 30mm × 30mm × 5mm through heat treated sintered compact, 5mm direction is magnetic field orientating direction, the magnet sandblasting after processing, and purge, after clean surface, is arranged on work rest, each work rest is installed one group of magnet (10).
Separately get the magnet (10) of one group of clean surface as blank example.
The work rest being fixed with magnet is sent into different coating chambers respectively, respectively with 0.5m in each coating chamber
3the speed of/hr passes into oxygen, and heats to 50 ~ 650 DEG C respectively, preoxidation 0.05 ~ 12 hour, and in this course, the relative humidity of coating chamber controls below 10%.
Close oxygen, coating chamber and evaporator room are evacuated to gauge pressure 10 respectively
-1~ 10
-2after Pa, metal M g is heated to 650 DEG C at evaporator room, delivers to coating chamber after forming Mg steam, to magnet evaporation 1 hour, in this course, the temperature of coating chamber controlled at 300 DEG C, and relative humidity controls below 10%.
Continue to keep coating chamber vacuum tightness to be gauge pressure 10
-1~ 10
-2pa, below Temperature fall to 50 DEG C, vacuum breaker, takes out workpiece, obtains after the polished finish of workpiece ball milling.
Magnetic property evaluation procedure: sintered magnet uses the NIM-10000H type BH block rare earth permanent magnetism nondestructive measurement system of metering institute of China to carry out magnetic property detection to often organizing magnet, evaluates mean value.
Bonding force grade adopts the bonding force test determines described in specification sheets.
The situation of the embodiment in different preoxidation situation and the magnetic property evaluation of comparative example and bonding force evaluation is as shown in table 2.
The situation that the magnetic property evaluation of table 2 embodiment and comparative example and bonding force are evaluated
So, obtain the MgO distribution thin layer of rare-earth magnet surface formation and the Mg layer outside this MgO distributes thin layer, the MO distribution laminate structure of embodiment 4 obtains the secondary electron image confirmation of FE-EPMA (electron probe microanalysis (EPMA)), and result as shown in fig. 1.The MO distribution laminate structure of embodiment 3,5,6,7,8 obtains FE-EPMA (electron probe microanalysis (EPMA)) equally and confirms (because above-mentioned collection of illustrative plates is extremely similar to the collection of illustrative plates of embodiment 4, no longer being repeated to enumerate at this).
Can see from table 2, be less than under the Pre oxidation of 100 DEG C or when preoxidation time is less than 0.1 hour, MgO distribution thickness of thin layer is not enough, and bonding force is weak, and coating is easily peeled off from magnet surface, can not effectively play a protective role; Larger impact can be subject to more than the performance of 600 DEG C of magnet at Pre oxidation; Preoxidation time is greater than the production cycle that 12 hours then have a strong impact on product.
In FIG, lines 1 represent the concentration distribution of Fe element in coating and substrate; Lines 2 represent the concentration distribution of O element in coating and substrate; Lines 3 represent the concentration distribution of Mg element in coating and substrate.
Embodiment two
Prepare rare-earth magnet sintered compact, this sintered compact has following atom composition: Dy is 5, Lu be 0.2, Er be 0.2, Nd be 8.5, Tm is 0.5, Y is 0.1, Co be 1, C be 0.05, B be 7, Cu is 0.2, Mn is 0.2, Ga be 0.2, Bi be 0.1, Ti be 0.3, Fe is surplus.Obtain according to the melting of existing rare-earth magnet, rejection tablet, hydrogen fragmentation, airflow milling, compacting, sintering and heat treated operation.
Be processed into the magnet of 30mm × 30mm × 8mm through heat treated sintered compact, 8mm direction is magnetic field orientating direction, the magnet sandblasting after processing, purge, after clean surface, after be arranged on work rest, each work rest is installed one group of magnet (10).
Separately get the magnet (10) of one group of clean surface as blank example.
The work rest being fixed with magnet is sent into different coating chambers respectively, respectively with 0.8m in each coating chamber
3the speed of/hr passes into oxygen, and heats to 300 DEG C, preoxidation 1 hour, and in this course, the relative humidity of coating chamber controls below 10%.
Close oxygen, coating chamber and evaporator room are evacuated to gauge pressure 10 respectively
-3~ 10
-4after Pa, the metal M g of weight ratio 1:1 and Zn is heated to 650 DEG C and 500 DEG C respectively at evaporator room, after forming Mg steam and Zn steam, delivers to coating chamber, evaporation 0.01 ~ 4 hour is distinguished to magnet, in this course, the temperature of coating chamber controls at 50 ~ 500 DEG C.
Continue to keep coating chamber vacuum tightness to be gauge pressure 10
-3~ 10
-4pa, below Temperature fall to 50 DEG C, vacuum breaker, takes out workpiece, obtains after the polished finish of workpiece ball milling.
Magnetic property evaluation procedure: sintered magnet uses the NIM-10000H type BH block rare earth permanent magnetism nondestructive measurement system of metering institute of China to carry out magnetic property detection to often organizing magnet, evaluates mean value.
Bonding force grade adopts the bonding force test determines described in specification sheets.
The situation of the embodiment in different preoxidation situation and the magnetic property evaluation of comparative example and bonding force evaluation is as shown in table 3.
The situation that the magnetic property evaluation of table 3 embodiment and comparative example and bonding force are evaluated
So, obtain MO distribution thin layer (M is the mixing of Mg and Zn) of rare-earth magnet surface formation and the M layer outside this MO distributes thin layer, the MO distribution laminate structure of embodiment 4,5,6,7,8 obtains the confirmation (because above-mentioned collection of illustrative plates is extremely similar to the collection of illustrative plates of embodiment 4 in embodiment one, no longer being repeated to enumerate at this) of FE-EPMA (electron probe microanalysis (EPMA)) equally.
Can see from table 3, at the deposited chamber temperature being less than 100 DEG C or when the evaporation time is less than 0.05 hour, MgO distribution thin layer spreading depth is not enough, and bonding force is weak, and coating is easily peeled off from magnet surface, can not effectively play a protective role; Larger impact can be subject to more than the performance of 400 DEG C of magnet in deposited chamber temperature; The evaporation time is greater than the production cycle that 3 hours then affect product, and causes energy consumption to increase.
Embodiment three
Prepare rare-earth magnet sintered compact, this sintered compact has following atom composition: Dy is 5, Lu be 0.2, Er be 0.2, Nd be 8.5, Tm is 0.5, Y is 0.1, Co be 1, C be 0.05, B be 7, Cu is 0.2, Mn is 0.2, Ga be 0.2, Bi be 0.1, Ti be 0.3, Fe is surplus.Obtain according to the melting of existing rare-earth magnet, rejection tablet, hydrogen fragmentation, airflow milling, compacting, sintering and heat treated operation.
Be processed into the magnet of 30mm × 30mm × 8mm through heat treated sintered compact, 8mm direction is magnetic field orientating direction, the magnet sandblasting after processing, and purge, after clean surface, is then arranged on work rest, and 10 magnet installed by work rest.
The work rest being fixed with magnet is sent into coating chamber, respectively with 1.0m in coating chamber
3the speed of/hr passes into oxygen, and heats to 200 DEG C, preoxidation 2 hours, and in this course, the relative humidity of coating chamber controls below 10%.
Close oxygen, coating chamber and evaporator room are evacuated to gauge pressure 10
-4~ 10
-5after Pa, metal M g is heated to 650 DEG C at evaporator room, delivers to coating chamber after forming Mg steam, to magnet evaporation 2 hours, in this course, the temperature of coating chamber controlled at 300 DEG C.
Afterwards, with 0.2m
3the speed of/hr passes into oxygen to coating chamber, and metal M g is heated to 650 DEG C at evaporator room, delivers to coating chamber after forming Mg steam, evaporation is continued 1 hour to magnet, in this course, the temperature of coating chamber controls at 300 DEG C, and relative humidity controls below 10%.
Below coating chamber Temperature fall to 50 DEG C, take out workpiece, obtain after the polished finish of workpiece ball milling.
So, obtain the MgO distribution thin layer that rare-earth magnet surface is formed, the Mg layer formed on this MgO distributes thin layer outside surface, and the MgO layer formed on the outside surface of Mg layer.After Mg layer outside surface forms MgO layer, effectively can extend magnet work-ing life.
Embodiment four
Prepare rare-earth magnet sintered compact, this sintered compact has following atom composition: Dy is 5, Lu be 0.2, Er be 0.2, Nd be 8.5, Tm is 0.5, Y is 0.1, Co be 1, C be 0.05, B be 7, Cu is 0.2, Mn is 0.2, Ga be 0.2, Bi be 0.1, Ti be 0.3, Fe is surplus.Obtain according to the melting of existing rare-earth magnet, rejection tablet, hydrogen fragmentation, airflow milling, compacting, sintering and heat treated operation.
Be processed into the magnet of 30mm × 30mm × 8mm through heat treated sintered compact, 8mm direction is magnetic field orientating direction, the magnet sandblasting after processing, and purge, after clean surface, is then arranged on work rest, and 10 magnet installed by work rest.
The work rest being fixed with magnet is sent into coating chamber, respectively with 1.0m in coating chamber
3the speed of/hr passes into oxygen, and heats to 200 DEG C, preoxidation 2 hours, and in this course, the relative humidity of coating chamber controls below 10%.
Close oxygen, coating chamber and evaporator room are evacuated to gauge pressure 10
-2~ 10
-3after Pa, metal M g is heated to 650 DEG C at evaporator room, delivers to coating chamber after forming Mg steam, to magnet evaporation 3 hours, in this course, the temperature of coating chamber controlled at 200 DEG C.
Heat-treat the workpiece completing evaporation, thermal treatment temp is 50 ~ 350 DEG C, and heat treatment time is 0.5 ~ 12h.
Continue to keep coating chamber vacuum tightness to be gauge pressure 10
-2~ 10
-3pa, below Temperature fall to 50 DEG C, vacuum breaker, takes out workpiece, obtains after the polished finish of workpiece ball milling.
Bonding force grade adopts the bonding force test determines described in specification sheets.
The situation that embodiment in different preoxidation situation and the magnetic property of comparative example are evaluated is as shown in table 4.
The situation of the bonding force evaluation of table 4 embodiment and comparative example
Above-described embodiment is only used for further illustrating several specific embodiment of the present invention; but the present invention is not limited to embodiment; every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all fall in the protection domain of technical solution of the present invention.
Claims (9)
1. a method for rare-earth magnet vacuum vapor plating, described rare-earth magnet is for containing R
2t
14the magnet of B principal phase, described R is selected from least one comprised in the rare earth element of yttrium, and described T is at least one transition metal comprising Fe, it is characterized in that, comprises the following steps:
1), after rare-earth magnet workpiece carries out pre-treatment, be contained on work rest;
2) described work rest is sent into reaction chamber, preoxidation, the Pre oxidation of described preoxidation is 100 ~ 600 DEG C, and preoxidation time is 0.1 ~ 12 hour, and relative humidity controls below 10%;
3) described work rest is sent into coating chamber, vacuumize, evaporation of metal material M is heated to vaporization temperature, carry out evaporation to described rare-earth magnet workpiece, described M is selected from least one of Mg, Al or Zn;
4) lower the temperature, vacuum breaker, takes out workpiece and obtains.
2. the method for a kind of vacuum vapor plating according to claim 1, is characterized in that: step 3) in, the evaporation time is 0.05 ~ 3 hour.
3. the method for a kind of vacuum vapor plating according to claim 1, is characterized in that: described rare-earth magnet is NdFeB based magnet.
4. the method for a kind of vacuum vapor plating according to claim 3, is characterized in that: step 2) described reaction chamber be directly used as step 3) described coating chamber, and in described step 2) complete after, close oxygen.
5. the method for a kind of vacuum vapor plating according to claim 1 and 2, is characterized in that: in step 3) after, be also provided with following step, continue to pass into O
2, evaporation of metal material M is heated to vaporization temperature simultaneously, to described workpiece evaporation 0.05 ~ 1 hour, the outside surface of M layer forms MO layer.
6. the method for a kind of vacuum vapor plating according to claim 1 and 2, it is characterized in that: in step 3) after, be also provided with following step, the workpiece completing evaporation is heat-treated, thermal treatment temp is 80 ~ 300 DEG C, and heat treatment time is 0.5 ~ 12h.
7. the method for a kind of vacuum vapor plating according to claim 4, is characterized in that: described evaporation of metal material is Mg, and the Schwellenwert of described vaporization temperature is 650 DEG C; Or described evaporation of metal material is Al, the Schwellenwert of described vaporization temperature is 980 DEG C; Or described evaporation of metal material is Zn, the Schwellenwert of described vaporization temperature is 500 DEG C; Or described evaporation of metal material be Mg, Al and Zn wherein two or three composition, the Schwellenwert of described vaporization temperature is above-mentioned differing materials vaporization temperature Schwellenwert separately.
8. the method for a kind of vacuum vapor plating according to claim 5, is characterized in that: step 3) in also evaporator room is set, the temperature of described evaporator room is the vaporization temperature of evaporating materials, and the temperature of described coating chamber controls at 200 ~ 400 DEG C.
9. cover a rare-earth magnet for evaporation coating, it is characterized in that: it is included in the MO distribution layer of rare-earth magnet surface formation and the M layer outside described MO distribution layer, and described M is selected from least one of Mg, Al or Zn.
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| CN107895644B (en) * | 2017-11-24 | 2019-10-01 | 北京七星华创磁电科技有限公司 | It is a kind of to expand the production line seeped and production method for heavy rare earth crystal boundary |
| CN109360728B (en) * | 2018-07-18 | 2020-12-01 | 浙江中科磁业有限公司 | Method for enhancing coercive force of neodymium iron boron magnet by evaporation crystal boundary diffusion |
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|---|---|---|---|---|
| EP1024506A1 (en) * | 1999-01-27 | 2000-08-02 | Sumitomo Special Metals Co., Ltd. | Rare earth metal-based permanent magnet, and process for producing the same |
| CN1900361A (en) * | 2006-07-14 | 2007-01-24 | 西南大学 | Process for preparing neodymium-iron-boron permanent magnetic material surface gradient function coating layer |
| CN102002671A (en) * | 2010-09-16 | 2011-04-06 | 耿学红 | Method for preventing NdFeB permanent magnet from being corroded |
| CN102758174A (en) * | 2012-07-02 | 2012-10-31 | 中国科学院宁波材料技术与工程研究所 | Protective film on surface of workpiece basal body and preparation method of protective film |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1024506A1 (en) * | 1999-01-27 | 2000-08-02 | Sumitomo Special Metals Co., Ltd. | Rare earth metal-based permanent magnet, and process for producing the same |
| CN1900361A (en) * | 2006-07-14 | 2007-01-24 | 西南大学 | Process for preparing neodymium-iron-boron permanent magnetic material surface gradient function coating layer |
| CN102002671A (en) * | 2010-09-16 | 2011-04-06 | 耿学红 | Method for preventing NdFeB permanent magnet from being corroded |
| CN102758174A (en) * | 2012-07-02 | 2012-10-31 | 中国科学院宁波材料技术与工程研究所 | Protective film on surface of workpiece basal body and preparation method of protective film |
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