A kind of bonded rare earth permanent magnetic alloy
Technical field
The present invention relates to the technical field of rare earth permanent-magnetic material, a kind of Nd-Fe-B system bonding rare earth permanent magnet material is particularly provided.
Background technology
Permanent magnetic material, as a kind of functional material be most widely used in modern industry and science and technology, mainly comprises Al-Ni-Co permanent magnet material, ferrite permanent-magnet materials, rare earth permanent-magnetic material and other permanent magnetic material etc.Wherein rare-earth permanent magnetic material is that the alloy that rare earth metal and transition metal are formed is made through certain technique, is the best class permanent magnetic material of current combination property.
And according to preparation method, Nd-Fe-Bo permanent magnet material can be divided into again sintered NdFeB and the large class of Agglutinate neodymium-iron-boron two.Wherein, although the magnetic property of sintered bond Nd-Fe-Bo permanent magnet material is very high, but coercive forces etc. are on the low side, corrosion resistance is poor, particularly processing characteristics wretched insufficiency, also can produce in sintering process and significantly shrink, cause its dimensional accuracy to ensure, the aftertreatment technologys such as usual needs grinding, make it be very restricted in the application.Binding Nd-Fe-B permanent magnetic material is then by NdFeB magnetic powder and resin, the binding agent such as macromolecular compound or the low-melting-point metal Homogeneous phase mixing such as plastics, then by compression, extrude or compound permanent magnetic material that the manufacturing process such as injection is made, compared with sintered Nd-Fe-B permanent magnetic material, although binding Nd-Fe-B permanent magnetic material magnetic property declines to some extent, but its stability is better, its magnet shape degree of freedom is good simultaneously, thin-walled can be made, small-sized, the product special-shaped and dimensional accuracy is high, in addition its density is little, cost is low, the feature that material recovery recycling is good, development in recent years is very fast, be widely used in stereo set, computer, the every field such as mobile communications tool.
But the preparation of Agglutinate neodymium-iron-boron material also also exists a lot of problem, first be exactly the contradiction existed between magnetic property and forming property, namely in order to improve the magnetic property of material as far as possible, wish the NdFeB magnetic powder addition as far as possible improved in composite permanent-magnetic material, but too high useful load will inevitably reduce the mobility of magnetic and binder mixtures, and then worsen the performances such as follow-up mixing, shaping.Such as carry out the ameliorative way such as couplant surface treatment for magnetic powder although have employed at present, the effect reached is still unsatisfactory.In addition because Magnaglo surface activity is very high, there is a large amount of micro-crack in broken, the quick-fried powder surface that causes of hydrogen in addition, makes powder very easily oxidized, thus improve the viscosity of mixture and affect formability etc.
How can obtain a kind of forming property of existing excellence, had again the binding Nd-Fe-B permanent magnetic material of excellent magnetic energy concurrently, be the Main way that people constantly pursue and study simultaneously always.
Summary of the invention
Namely object of the present invention is the formability providing a kind of existing excellence, has again the Nd-Fe-B system bonding rare earth permanent magnet material of excellent magnetic property.
The Nd-Fe-B system bonded rare earth permanent magnetic alloy powder used in the present invention has following composition: in atomic percentage conc, Nd15.0-18.0, B5.0-6.0, Al0.2-0.3, Co7.0-10.0, Nb0.5-0.8, Zr0.1-0.3, Cu0.2-0.4, Dy3.0-5.0, surplus is Fe and inevitable impurity.
The concrete preparation method of the Nd-Fe-B system bonded rare earth permanent magnetic alloy in the present invention is as follows:
1) melting, the alloy raw material be equipped with is put into vacuum induction melting furnace, smelting furnace is evacuated to 15-20Pa and heat melting until temperature to 1150 DEG C time to start to be filled with argon gas to pressure be 0.3-0.4MPa, be warming up to 1350-1400 DEG C of refining 5-10 minute subsequently, insulation leaves standstill 1-1.5 minute;
2) pour into a mould, adopt the method for getting rid of Strip casting, chill roll diameter is 500mm, and controlled cooling model speed, at 2.7m/s-3m/s, obtains the slab that thickness is 0.2-0.4mm;
3) Mechanical Crushing, obtains by Mechanical Crushing the meal that particle diameter is 100-200 μm by slab;
4) hydrogen is quick-fried, be that meal Mechanical Crushing obtained under the condition of 1-2L/min is heated to 800-820 DEG C at hydrogen flowing quantity, after insulation 5-10min, increase hydrogen flowing quantity to keep to 3-4L/min, inhale hydrogen 2-3h, arrange hydrogen subsequently and be filled with argon gas, starting to vacuumize dehydrogenation when argon pressure reaches 0.8-1MPa, during to vacuum degree 2-4Pa, dehydrogenation terminates;
5) grind, adopt airflow milling to grind, specifically add the zinc stearate of 0.10-0.13wt%, in nitrogen atmosphere, be crushed to average grain diameter is 30-50 μm, obtains fine powder.
6) preliminary treatment, by fine powder with dimethylacetylamide be solvent polyamide-imide resin solution mixing and stirring after, be heated to 150-180 DEG C, solvent volatilized and obtains cured film on magnetic surface.
7) mixing, by the magnetic after overlay film and polyamide binding agent and add auxiliary agent and mix, carry out mixing in twin shaft mixing roll, melting temperature is 200-220 DEG C, mixing time 30-40min.
8) injection moulding, is preheating to 100-120 DEG C by mold temperature, injection temperature 240-260 DEG C, is shaped and pressurize, obtains Nd-Fe-B system of the present invention bonded rare earth permanent magnetic alloy at the magnetic field intensity of 1800-2000kA/m, the injection pressure hemostasis of 20-25MPa.
The invention has the advantages that: (1) appropriate design composition of alloy, by rational proportion that is light, heavy rare earth, and the appropriateness of other alloying elements is added, and obtains the RE permanent magnetic alloy of optimal performance; (2) have employed suitable melting, disintegrating process obtains bonding Magnaglo; (3) have employed suitable preliminary treatment, thermoplastic resin binder and interpolation auxiliary agent, and corresponding calendering process, obtain high charging ratio and have excellent formability can melt flow stream; (4) have employed advanced injection molding process, prepare the Nd-Fe-B system bonded rare earth permanent magnetic alloy of excellent performance.
Embodiment
Embodiment 1-4, and comparative example 1-3:
1) melting, the alloy raw material be equipped with by composition in table 1 is put into vacuum induction melting furnace, smelting furnace is evacuated to 18Pa and heat melting until temperature to 1150 DEG C time to start to be filled with argon gas to pressure be 0.4MPa, be warming up to 1380 DEG C of refinings 8 minutes subsequently, insulation leaves standstill 1.5 minutes;
2) pour into a mould, adopt the method for getting rid of Strip casting, chill roll diameter is 500mm, and controlled cooling model speed, at 2.8m/s, obtains the slab that thickness is 0.3mm;
3) Mechanical Crushing, obtains by Mechanical Crushing the meal that particle diameter is 150 μm by slab;
4) hydrogen is quick-fried, be that meal Mechanical Crushing obtained under the condition of 1.5L/min is heated to 820 DEG C at hydrogen flowing quantity, after insulation 8min, increase hydrogen flowing quantity to keep to 4L/min, inhale hydrogen 3h, arrange hydrogen subsequently and be filled with argon gas, starting to vacuumize dehydrogenation when argon pressure reaches 0.9MPa, during to vacuum degree 3Pa, dehydrogenation terminates;
5) grind, adopt airflow milling to grind, specifically add the zinc stearate of 0.12wt%, in nitrogen atmosphere, be crushed to average grain diameter is 40 μm, obtains fine powder.
6) preliminary treatment, by fine powder with dimethylacetylamide be solvent polyamide-imide resin solution mixing and stirring after, be heated to 150 DEG C, solvent volatilized and obtains cured film on magnetic surface; Wherein the mixing addition of polyamide-imide resin is 1 part relative to magnetic powder 100 weight portion.
7) mixing, by the magnetic after overlay film and polyamide binding agent and add auxiliary agent and mix, carry out mixing in twin shaft mixing roll, melting temperature is 200 DEG C, and mixing time is 30min, wherein, described polyamide to be molecular weight be 15000 nylon 6, its addition is 3 parts relative to the Magnaglo of 100 weight portions, and described interpolation auxiliary agent is 2,6-DI-tert-butylphenol compounds and active carbon, its addition is respectively 0.8 part and 1 part relative to the Magnaglo of 100 weight portions.
8) injection moulding, mold temperature is preheating to 100 DEG C, injection temperature 240 DEG C, is shaped and pressurize at the magnetic field intensity of 1800kA/m, the injection pressure hemostasis of 20MPa, obtains the Nd-Fe-B system bonded rare earth permanent magnetic alloy of embodiment of the present invention 1-4 and comparative example 1-3.
In described alloying element, Nd, Fe and B are the basic elements forming neodymium iron boron principal phase, must ensure that the content of Nd is more than 15.0, otherwise will be difficult to effectively form RE permanent magnetic alloy, but its content can not be too high, otherwise will the interpolation quantity of other elements be limited and affect the performance of alloy monolithic.B is also the basic composition element of principal phase, and its content should more than 5.0, but too much interpolation can cause the deterioration of magnetic property.
Aluminium element can play significantly and improve coercitive effect, useful effect is played for the processing characteristics improving alloy simultaneously, but excessive interpolation there is no benefit for coercitive raising, can cause the remarkable decline of remanent magnetism on the contrary, the Al in alloy system of the present invention should in the scope of 0.2-0.3.
Cobalt element obviously can improve the Curie temperature of alloy system, but the interpolation of cobalt obviously can cause the decline of the performance such as remanent magnetism, coercive force, therefore the addition of cobalt element must strictly be controlled, play for the enough raising effects of Curie temperature to make it, its addition at least should be 7.0, simultaneously in order to limit the side effect that it adds, its content should be controlled below 10.0.
Niobium and zirconium are all the elements of typical inhibiting grain growth, inhibiting grain growth can be played in alloy system, improve the effects such as squareness, it adds deficiency of content will affect magnetic form anisotropy in dehydrogenation regrouping process, thus the remarkable deficiency of alloy system magnetic property after causing being shaped.
Copper can avoid principal phase for the excessively solid solution mutually of rich neodymium, thus significantly improves coercive force, but the interpolation of too much copper then can affect the level and smooth of main phase grain, thus significantly falls low-alloyed magnetic property.In addition, copper can also play the effect suppressing cobalt to worsen magnetic property to a certain extent.
The interpolation of heavy rare earth element dysprosium can improve the coercive force of alloy system significantly, but its too much interpolation can worsen the performances such as the remanent magnetism of alloy, and therefore limiting its addition is 3.0-5.0.
Table 1
RE permanent magnetic alloy system in the application, by the coordinative role between alloying element, the unforeseeable comprehensive magnetic energy obtaining excellence.
Embodiment 5-6, and comparative example 4-9, the chemical composition of alloy is identical with embodiment 2, the paper examines impact of preparation technology for alloy property, design parameter and test result are see table 2, wherein A represents the interpolation number of polyamide-imides, B represents the interpolation number of nylon 6/poly amide resin, C represents 2, the interpolation number of 6-DI-tert-butylphenol compounds, D represents the interpolation number of active carbon, E represents pretreated heating-up temperature (DEG C), F represents the temperature (DEG C) of injection moulding, G represents the pressure (MPa) of injection moulding, H represents that temperature is 250 DEG C, pressure is 100kgf/cm
2, the fluidity of molten (g/10min) of the mixing constituent of magnetic that records of Φ 1mm × 7mm mouth mould, I is the remanent magnetism (T) of permanent magnetic material, J is that permanent magnetic material is soaked in corrosion resistance test result in 5%NaCl salt solution after 24h (zero is no corrosion, × for there being obvious corrosion).
Table 2
As can be seen from the result of table 2, polyamide-imides overlay film has material impact for the mobility of magnetic/thermoplastic resin binder's mixture, and this mainly comes from intermiscibility good between polyamide-imides and polyamide thermoplastic resin; Meanwhile, polyamide-imides mechanical strength and heat resistance also improve corrosion resistance and the antioxygenic property of material to a certain extent.For playing above-mentioned effect, the addition of polyamide-imides at least should be 1.0 parts, but too high addition can increase the viscosity of system on the contrary and reduces the mobility of melt thus worsen forming property.
In addition the pretreated heating-up temperature of polyamide-imides overlay film also has material impact for the performance of overlay film, in order to ensure the abundant volatilization dimethylacetylamide of solvent and make polyamide-imides that certain polymerization reaction occur and the overlay film that obtains hardening, to reach the object providing mobility, heating-up temperature should at least reach 150 DEG C, but during more than 180 DEG C, the effect that too high heating-up temperature has not improved further for fluidity of molten.
The addition of nylon 6/poly amide resin is limited in the scope of 3-5 part.If addition is less than 3 parts, by causing, the mixing resistance of mixed system is excessive, and mobility is too low, thus make forming difficulty, conversely, if its addition is excessive, such as more than 5 parts, then do not reach the present invention improve Magnaglo useful load and improve magnetism of material can object.Meanwhile, in order to ensure the mechanical strength of material, the number-average molecular weight that should limit nylon 6/poly amide resin is greater than 12000, but can not be too high, if more than 18000, then can cause the remarkable reduction of mobility, thus worsens the forming property of system.
2,6-DI-tert-butylphenol compounds mainly plays two effects in system, first is the oxidation preventing mixing process and product, second is the performance improving injection moulding, for playing above-mentioned effect, 2, the addition of 6-DI-tert-butylphenol compounds should at least reach 0.8 part, but can not be too high, too high meeting causes the mechanical property of formed product to worsen, and limits its addition for this reason and is less than 1 part.
Active carbon can effectively play heavy metal ion such as preventing Fe, Co and be oxidized, for playing above-mentioned effect, the addition of preferred active carbon should be at least 1 part, but too much active carbon addition can the mobility of serious reduction system, also can affect the fabrication strength of system, therefore should control its addition below 1.4 parts.Meanwhile, in order to obtain the performance of enough Adsorption of Heavy Metal Ions, and avoiding it to reduce magnetic property for the anisotropic impact of magnetic, requiring that the particle diameter of active carbon is below 80 μm.
Injection temperature and injection pressure have material impact for the final forming quality of material and magnetic property, injection temperature and injection pressure too low, the illiquidity of fluid, packed density can be caused too low, thus worsen mechanical property and the magnetic property of moulding material, but temperature is too high, then may cause resin glue that unnecessary being cross-linked occurs, and cause the cracking of moulding material, thus affect the performance of material.
To sum up, reasonably combined by alloying element of the present invention, and suitable preparation technology, by injection molding process, prepared magnetic property and decay resistance all very excellent Nd-Fe-B system bonded rare earth permanent magnetic alloy.